Sample records for apatites

Certain complex structures are logically regarded as intergrowths of chemically or topologically discrete modules. When the proportions of these components vary systematically a polysomatic series is created, whose construction provides a basis for understanding defects, symmetry alternation and trends in physical properties. Here, we describe the polysomatic family A(5N)B(3N)O(9N + 6)X(Ndelta) (2 < or = N < or = infinity) that is built by condensing N apatite modules (A(5)B(3)O(18)X(delta)) in configurations to create B(n)O(3n + 1) (1 < or = n < or = infinity) tetrahedral chains. Hydroxyapatite [Ca(10)(PO(4))(6)(OH)(2)] typifies a widely studied polysome where N = 2 and the tetrahedra are isolated in A(10)(BO(4))(6)X(2) compounds, but N = 3 A(15)(B(2)O(7))(3)(BO(4))(3)X(3) (ganomalite) and N = 4 A(20)(B(2)O(7))(6)X(4) (nasonite) are also known, with the X site untenanted or partially occupied as required for charge balance. The apatite modules, while topologically identical, are often compositionally or symmetrically distinct, and an infinite number of polysomes is feasible, generally with the restriction being that an A:B = 5:3 cation ratio be maintained. The end-members are the N = 2 polysome with all tetrahedra separated, and N = infinity, in which the hypothetical compound A(5)B(3)O(9)X contains infinite, corner-connected tetrahedral strings. The principal characteristics of a polysome are summarized using the nomenclature apatite-(A B X)-NS, where A/B/X are the most abundant species in these sites, N is the number of modules in the crystallographic repeat, and S is the symmetry symbol (usually H, T, M or A). This article examines the state-of-the-art in polysomatic apatite synthesis and crystallochemical design. It also presents X-ray and neutron powder diffraction investigations for several polysome chemical series and examines the prevalence of stacking disorder by electron microscopy. These insights into the structure-building principles of apatite

Recent discoveries of water-rich lunar apatite are more consistent with the hydrous magmas of Earth than the otherwise volatile-depleted rocks of the Moon. Paradoxically, this requires H-rich minerals to form in rocks that are otherwise nearly anhydrous. We modeled existing data from the literature, finding that nominally anhydrous minerals do not sufficiently fractionate H from F and Cl to generate H-rich apatite. Hydrous apatites are explained as the products of apatite-induced low magmatic fluorine, which increases the H/F ratio in melt and apatite. Mare basalts may contain hydrogen-rich apatite, but lunar magmas were most likely poor in hydrogen, in agreement with the volatile depletion that is both observed in lunar rocks and required for canonical giant-impact models of the formation of the Moon. PMID:24652938

The objective of this errata report is to document an error in the apatite loading (i.e., treatment capacity) estimate reported in previous apatite treatability test reports and provide additional calculation details for estimating apatite loading and barrier longevity. The apatite treatability test final report (PNNL-19572; Vermeul et al. 2010) documents the results of the first field-scale evaluation of the injectable apatite PRB technology. The apatite loading value in units of milligram-apatite per gram-sediment is incorrect in this and some other previous reports. The apatite loading in units of milligram phosphate per gram-sediment, however, is correct, and this is the unit used for comparison to field core sample measurements.

Apatite crystals from two types of samples were analyzed by electron microprobe for 15 major and trace elements: (1) apatite in H2O- and S-saturated experimental charges of the 1982 El Chicho??n trachyandesite and (2) apatite in volcanic rocks erupted from 20 volcanoes. The SO3 contents of the experimental apatite increase with increasing oxygen fugacity (fo2), from ???0.04 wt% in reduced charges buffered by fayalite-magnetite-quartz (FMQ), to 1.0-2.6 wt% in oxidized charges buffered by manganosite-hausmanite (MNH) or magnetite-hematite (MTH). The SO3 contents of MNH- and MTH-buffered apatite also generally increase with increasing pressure from 2 to 4 kbar and decreasing temperature from 950 to 800??C. The partition coefficient for SO3 between apatite and oxidized melt increases with decreasing temperature but appears to be independent of pressure. Apatites in volcanic rocks show a wide range of SO3 contents (<0.04 to 0.63 wt%). Our sample set includes one group known to contain primary anhydrite and a second group inferred to have been free of primary anhydrite. No systematic differences in apatite S contents are observed between these two groups. Our study was initiated to define the factors controlling S contents in apatite and to evaluate the hypothesis that high S contents in apatite could be characteristic of S-rich anhydrite-bearing magmas such as those erupted from El Chicho??n in 1982 and Pinatubo in 1991. This hypothesis is shown to be invalid, probably chiefly a consequence of the slow intra-crystaline diffusion that limits re-equilibration between early formed apatite and the evolving silicate melt. Contributing factors include early crystallization of most apatite over a relatively small temperature interval, common late-stage magmatic enrichment of S, progressive oxidation during magmatic evolution, and strong controls on S contents in apatite exerted fo2, temperature, and pressure.

Materials with apatite crystal structure have applications ranging from biomaterials to electrolytes for solid oxide fuel cells. Their chemical flexibility and structural diversity provide a fertile ground to tune functionalities as potential candidates for many applications. However, magnetic apatites are rare. In this work, we use machine learning methods to rapidly screen a vast chemical space and identify novel apatite compositions with magnetic ions. We first construct a database of known materials from surveying the experimental literature. We then augment the database with features that capture the trends in geometry and bonding characteristics of apatites. Supervised classification learning form the basis of our machine learning approach through which we uncover design rules that enable prediction of potentially stable magnetic apatite compositions, prior to experimental synthesis. Finally, we validate our predictions using density functional theory calculations.

Apatite is one of the minerals that is rarely utilized in U-Pb geochronology, compared to some other U-rich accessory phases. Relatively low U concentration, commonly high proportion of common Pb and low closure temperature of U-Pb system of apatite inhibit its application as geochronological tool when other minerals such as zircon are widely available. However, zircon appear to be restricted to certain type of lunar rocks, carrying so called KREEP signature, whereas apatite (and whitlockite) is a common accessory mineral in the lunar samples. Therefore, utilizing apatite for lunar chronology may increase the pool of rocks that are available for U-Pb dating. The low stability of U-Pb systematics of apatite may also result in the resetting of the system during meteoritic bombardment, in which case apatite may provide an additional tool for the study of the impact history of the Moon. In order to investigate these possibilities, we have analysed apatites and zircons from two breccia samples collected during the Apollo 14 mission. Both samples were collected within the Fra Mauro formation, which is interpreted as a material ejected during the impact that formed the Imbrium Basin.

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl

It is well known that organic molecules from the vertebrate extracellular matrix of calcifying tissues are essential in structuring the apatite mineral. Here, we show that water also plays a structuring role. By using solid-state nuclear magnetic resonance, wide-angle X-ray scattering and cryogenic transmission electron microscopy to characterize the structure and organization of crystalline and biomimetic apatite nanoparticles as well as intact bone samples, we demonstrate that water orients apatite crystals through an amorphous calcium phosphate-like layer that coats the crystalline core of bone apatite. This disordered layer is reminiscent of those found around the crystalline core of calcified biominerals in various natural composite materials in vivo. This work provides an extended local model of bone biomineralization. PMID:24193662

Apatites of various chemistries are potentially important in chemical synthesis, clean energy and environmental remediation. The so-called 'lacunary' apatites are prospective fuel cell electrolytes, while silver analogues are potential photocatalysts, and radiation resistant silicate apatites can retain nuclear wastes. Although apatites have one-dimensional channels, as distinct from the three-dimensional channels in classic zeolites, they do display several zeolitic features including: a framework which can be tuned to accommodate different tunnel contents; an ability to accept large cations of different valance through the introduction of framework counter ions; and reversible ion exchange for some anions and cations. Most recently, it has been recognized, in both natural and synthetic materials, that intergrowth of tunnels of different size at the nanoscale is possible, a feature with important technology performance implications. This paper describes a new approach for the structural derivation of apatites from an idealized prototype that correlates chemistry and tunnel geometry, and in so doing, permits the design of new apatites and prediction of their properties.

Calcium phosphate apatites are inorganic compounds encountered in many different mineralized tissues. Bone mineral, for example, is constituted of nanocrystalline nonstoichiometric apatite, and the production of “analogs” through a variety of methods is frequently reported. In another context, the ability of solid surfaces to favor the nucleation and growth of “bone-like” apatite upon immersion in supersaturated fluids such as SFB is commonly used as one evaluation index of the “bioactivity” of such surfaces. Yet, the compounds or deposits obtained are not always thoroughly characterized, and their apatitic nature is sometimes not firmly assessed by appropriate physicochemical analyses. Of particular importance are the “actual” conditions in which the precipitation takes place. The precipitation of a white solid does not automatically indicate the formation of a “bone-like carbonate apatite layer” as is sometimes too hastily concluded: “all that glitters is not gold.” The identification of an apatite phase should be carefully demonstrated by appropriate characterization, preferably using complementary techniques. This review considers the fundamentals of calcium phosphate apatite characterization discussing several techniques: electron microscopy/EDX, XRD, FTIR/Raman spectroscopies, chemical analyses, and solid state NMR. It also underlines frequent problems that should be kept in mind when making “bone-like apatites.” PMID:23984373

Apatite was analyzed by electron microprobe in 3 cumulate and 10 basaltic eucrites. Eucritic apatite is fluorine-rich with minor chlorine and hydroxyl (calculated by difference). We confirmed the hydroxyl content by measuring hydroxyl directly in apatites from three representative eucrites using secondary ionization mass spectroscopy. Overall, most eucritic apatites resemble fluorine-rich lunar mare apatites, but intriguing OH- and Cl-rich apatites suggest a role for water and/or hydrothermal fluids in the Vestan interior or on other related differentiated asteroids. Most late-stage apatite found in mesostasis has little hydroxyl or chlorine and is thought to have crystallized from a degassed magma; however, several apatites exhibit atypical compositions and/or textural characteristics. For example, the isotopically anomalous basaltic eucrite Pasamonte has apatite in the mesostasis with significant OH. Apatites in Juvinas also have significant OH and occur as veinlets crosscutting silicates. Euhedral apatites in the Moore County cumulate eucrite occur as inclusions in pyroxene and are also hydroxyl-rich (0.62 wt% OH). The OH was confirmed by SIMS analysis and this apatite clearly points to the presence of water, at least locally, in the Vestan interior. Portions of Elephant Moraine (EET) 90020 have large and abundant apatites, which may be the product of apatite accumulation in a zone of melt-rock reaction. Relatively chlorine-rich apatites occur in basaltic eucrite Graves Nunataks (GRA) 98098 (approximately 1 wt% Cl). Particularly striking is the compositional similarity between apatite in GRA 98098 and apatites in lunar KREEP, which may indicate the presence of residual magmas from an asteroid-wide magma ocean on Vesta.

The ultrastructure of nanoscale apatite biomimetically formed on an organic template from a supersaturated mineralizing solution was studied to examine the morphological and crystalline arrangement of mineral apatites. Needle-shaped apatite crystal plates with a size distribution of ~100 to ~1000 nm and the long axis parallel to the c axis ([002]) were randomly distributed in the mineral films. Between these randomly distributed needle-shaped apatite crystals, amorphous phases and apatite crystals (~20–40 nm) with the normal of the grains quasi-perpendicular to the c axis were observed. These observations suggest that the apatite film is an interwoven structure of amorphous phases and apatite crystals with various orientations. The mechanisms underlying the shape of the crystalline apatite plate and aggregated apatite nodules are discussed from an energy-barrier point of view. The plate or needle-shaped apatite is favored in single-crystalline form, whereas the granular nodules are favored in the polycrystalline apatite aggregate. The similarity in shape in both single-crystalline needle-shaped apatite and polycrystalline granular apatite over a wide range of sizes is explained by the principle of similitude, in which the growth and shape are determined by the forces acting upon the surface area and the volume. PMID:19763228

We report a study on calibration of infrared (IR) method to determine water concentration in apatite using the elastic recoil detection (ERD) method. The calibration will allow us to constrain water content in lunar and martian apatites using IR spectra.

Lead contamination is of environmental concern due to its effect on human health. he purpose of this study was to develop a technology to immobilize Pb in situ in contaminated soils and wastes using apatite. ydroxyapatite [Ca10(PO4)6(OH)2]was reacted with aqueous Pb, resinexchang...

Lead contamination is of environmental concern due to its effect on human health. The purpose of this study was to develop a technology to immobilize Pb in situ in contaminated soils and wastes using apatite. Hydroxyapatite [Ca10(PO4)6(O...

Phosphorus (P) is an important and limiting element for life. One strategy for storing ortho phosphates (Pi) is polymerization. Polymerized Pi's (polyphosphates: (PO3-)n: polyPs) serve as a Pi bank, as well as a catiion chelator, energy source, & regulator of responses to stresses in the stationary phase of culture growth and development1. PolyP biochemistry has been investigated in yeasts, bacteria & plants2. Bigeochemical cycling of P includes the condensation of Pi into pyro (P2O7-4), & polyPs, & the release of Pi from these compounds by the hydrolytic degradation of Pi from phosphomonoester bonds. Alkaline phosphatase (ALP) is one of the predominate enzymes for regenerating Pi in aquatic systems3, & it cleaves Pi from polyPs. ALP is also the enzyme associated with apatite biomineralization in vertebrates4. PolyP was proposed to be the ALP substrate in bone mineralization5. Where calcium ions are plentiful in many aquatic environments, there is no requirement for aquatic life to generate Ca-stores. However, terrestrial vertebrates benefit from a bioavailable Ca-store such as apatite. The Pi storage strategy of polymerizing PO4-3 into polyPs dovetails well with Ca-banking, as polyPs sequester Ca, forming a neutral calcium polyphosphate (Ca-polyP: (Ca(PO3)2)n) complex. This neutral complex represents a high total [Ca+2] & [PO4-3], without the threat of inadvertent apatite precipitation, as the free [Ca+2] & [PO4-3], and therefore apatite saturation, are zero. Recent identification of polyP in regions of bone resorption & calcifying cartilage5 suggests that vertebrates may use polyP chemistry to bank Ca+2 and PO4-3. In vitro experiments with nanoparticulate Ca-polyP & ALP were undertaken to determine if carbonated apatite could precipitate from 1M Ca-polyP in Pi-free “physiological fluid” (0.1 M NaCl, 2 mM Ca+2, 0.8 mM Mg+2, pH ~8.0 ±0.5, 37 °C), as this is estimated to generate the [Ca+2] & [PO4-3] required to form the apatite content of bone tissue

Using electron microprobe (EMP) and laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to collect major and rare-earth elements (REE), respectively, from apatites from the 1991 Mt. Pinatubo juvenile eruption products, we have determined that two statistically distinct populations of apatite exist. One population crystallized from the juvenile basaltic melt (basalt apatites) and the other population crystallized from the main dacitic magma body (silicic apatites). Both populations contain high-S apatites (> 0.7 wt.% SO3). Apatite has previously been shown to be a potential monitor for magmatic sulfur contents via numerous proposed coupled substitutions of P5 + for S6 +. However, simple apatite/melt partitioning cannot account for high-S silicic apatites, which grew from a silicic melt with an apparent maximum S concentration of ~ 80 ppm. Disparate apatite morphology (i.e. skeletal and acicular for basalt apatites and euhedral for silicic apatites) as well as compositional evidence reveal that high-S silicic apatites were not inherited from the juvenile basalt during mingling/mixing prior to eruption. Sulfur gain from neighboring anhydrite phenocrysts can also be ruled-out as a source of high sulfur. EMP sulfur mapping of silicic apatites shows highly irregular patterns of sulfur enrichment that do not correspond with adjacent anhydrite and can be found within apatites hosted by other minerals (e.g. hornblende and Fe-Ti oxides). With these data in mind, we propose high-S silicic apatites from Pinatubo and other sulfur-rich systems achieved elevated sulfur concentrations during high sulfur fluxing events that originated from underplated basalt during degassing of a SO2-rich fluid phase. That basalts were indeed sulfur rich and oxidized is here indicated by high S contents of apatites growing in basalt. The predominant location of S-rich areas of silicic apatite is crystal interiors of apatite inclusions in other mineral phases, while large apatite

The Moon is thought to be depleted relative to the Earth in volatile elements such as H, Cl and the alkalis. Nevertheless, evidence for lunar explosive volcanism has been used to infer that some lunar magmas exsolved a CO-rich and CO(2)-rich vapour phase before or during eruption. Although there is also evidence for other volatile species on glass spherules, until recently there had been no unambiguous reports of indigenous H in lunar rocks. Here we report quantitative ion microprobe measurements of late-stage apatite from lunar basalt 14053 that document concentrations of H, Cl and S that are indistinguishable from apatites in common terrestrial igneous rocks. These volatile contents could reflect post-magmatic metamorphic volatile addition or growth from a late-stage, interstitial, sulphide-saturated melt that contained approximately 1,600 parts per million H(2)O and approximately 3,500 parts per million Cl. Both metamorphic and igneous models of apatite formation suggest a volatile inventory for at least some lunar materials that is similar to comparable terrestrial materials. One possible implication is that portions of the lunar mantle or crust are more volatile-rich than previously thought. PMID:20651686

The transition from invertebrate calcium carbonate-based calcite and aragonite exo- and endoskeletons to the calcium phosphate-based vertebrate backbones and jaws composed of microscopic hydroxyapatite crystals is one of the great revolutions in the evolution of terrestrial organisms. To identify potential factors that might have played a role in such a transition, three key domains of the vertebrate tooth enamel protein amelogenin were probed for calcium mineral/protein interactions and their ability to promote calcium phosphate and calcium carbonate crystal growth. Under calcium phosphate crystal growth conditions, only the carboxy-terminus augmented polyproline repeat peptide, but not the N-terminal peptide nor the polyproline repeat peptide alone, promoted the formation of thin and parallel crystallites resembling those of bone and initial enamel. In contrast, under calcium carbonate crystal growth conditions, all three amelogenin-derived polypeptides caused calcium carbonate to form fused crystalline conglomerates. When examined for long-term crystal growth, polyproline repeat peptides of increasing length promoted the growth of shorter calcium carbonate crystals with broader basis, contrary to the positive correlation between polyproline repeat element length and apatite mineralization published earlier. To determine whether the positive correlation between polyproline repeat element length and apatite crystal growth versus the inverse correlation between polyproline repeat length and calcium carbonate crystal growth were related to the binding affinity of the polyproline domain to either apatite or carbonate, a parallel series of calcium carbonate and calcium phosphate/apatite protein binding studies was conducted. These studies demonstrated a remarkable binding affinity between the augmented amelogenin polyproline repeat region and calcium phosphates, and almost no binding to calcium carbonates. In contrast, the amelogenin N-terminus bound to both carbonate

The objective of this work was to develop nanocrystalline apatite (Ap) dispersed in a chitosan (CHI) matrix as a material for applications in bone tissue engineering. CHI/Ap composites of different weight ratios (20/80, 50/50 and 80/20) and with CHI of different molecular weights were prepared by a biomimetic stepwise route. Firstly, CaHPO(4).2H(2)O (DCPD) crystals were precipitated from Ca(CH(3)COO)(2) and NaHPO(4) in the bulk CHI solution, followed by the formation of CHI/DCPD beads by coacervation. The beads were treated with Na(3)PO(4)/Na(5)P(3)O(10) solution (pH 12-13) to crosslink the CHI and to hydrolyse the DCPD to nanocrystalline Ap. This new experimental procedure ensured that complete conversion of DCPD into sodium-substituted apatite was achieved without appreciable increases in its crystallinity and particle size. In addition, composites with silicon-doped Ap were prepared by substituting Na(3)PO(4) by Na(2)SiO(3) in the crosslinking/hydrolysis step. Characterization of the resultant composites by scanning electron microscopy, X-ray powder diffraction (XRD), thermal analysis and Fourier transform infrared spectroscopy confirmed the formation, within the CHI matrix, of nanoparticles of sodium- and carbonate-substituted hydroxyapatite [Ca(10-x)Na(x)(PO(4))(6-x)(CO(3))(x)(OH)(2)] with diameters less than 20nm. Relatively good correspondence was shown between the experimentally determined inorganic content and that expected theoretically. Structural data obtained from its XRD patterns revealed a decrease in both crystal domain size and cell parameters of Ap formed in situ with increasing CHI content. It was found that the molecular weight of CHI and silicate doping both affected the nucleation and growth of apatite nanocrystallites. These effects are discussed in detail. PMID:19632363

Apatite (Ca5(PO4)3(F,Cl,OH)) is one the most abundant halogen containing minerals in the crust. It is present in many different rock types and stable up to P-T conditions of the mantle. Although probably not relevant for the halogen budget of the mantle, apatite is potentially a carrier phase of halogens into the mantle via subduction processes and therefore important for the global halogen cycle. Different partitioning behavior of the halogens between apatite and melt/fluids causes fractionation of these elements. In hydrothermal environments apatite reacts via a coupled dissolution-reprecipitation process that leads to apatite halogen compositions which are in (local) equilibrium with the hydrothermal fluid. This behavior enables apatite to be used as fluid probe and as a tool for tracking fluid evolution during fluid-rock interaction. Here, we present a combined experimental and field related study focused on replacement of apatite under hydrothermal conditions, to investigate the partitioning of halogens between apatite and fluids. Experiments were conducted in a cold seal pressure apparatus at 0.2 GPa and temperatures ranging from 400-700°C using halogen bearing solutions of different composition (KOH, NaF, NaCl, NaBr, NaI) to promote the replacement of Cl-apatite. The halogen composition of reacted apatite was analyzed by electron microprobe (EMPA) and secondary ion mass spectrometry (SIMS). The data was used to calculate partition coefficients of halogens between fluid and apatite. Our new partitioning data show that fluorine is the most compatible halogen followed by chlorine, bromine and iodine. Comparison between partition coefficients of the apatite-fluid system and coefficients derived in the apatite-melt system reveals values for F that are one to two orders of magnitude higher. In contrast, Cl and Br show a similar partition behavior in fluid and melt systems. Consequently, apatite that formed by fluid-rock interaction will fractionate F from Cl more

The paper deals with the study of processing apatite ores with nitric acid and extraction of the rare earth elements. The rare earth elements can be successfully separated and recovered by extraction from the nitrate- phosphate solution, being an tributyl phosphate as extraction agent. The developed scheme of the processing apatite concentrate provides obtaining rare earth concentrates with high qualitative characteristics.

Nanocrystals of apatitic calcium phosphate impart the organic-inorganic nanocomposite in bone with favorable mechanical properties. So far, the factors preventing crystal growth beyond the favorable thickness of ca. 3 nm have not been identified. Here we show that the apatite surfaces are studded with strongly bound citrate molecules, whose signals have been identified unambiguously by multinuclear magnetic resonance (NMR) analysis. NMR reveals that bound citrate accounts for 5.5 wt% of the organic matter in bone and covers apatite at a density of about 1 molecule per (2 nm){sup 2}, with its three carboxylate groups at distances of 0.3 to 0.45 nm from the apatite surface. Bound citrate is highly conserved, being found in fish, avian, and mammalian bone, which indicates its critical role in interfering with crystal thickening and stabilizing the apatite nanocrystals in bone

CO2 plays a fundamental role in the evolution of magmatic and volcanic systems, but its low solubility in silicate melts means that direct records of magmatic CO2 concentrations remain elusive. The phosphate mineral apatite is unique among igneous minerals in its capacity to accommodate all major magmatic volatiles (H2O, F, Cl, CO2 and S). Although interest in apatite as a tool for tracking magmatic volatile contents (namely H2O, F, and Cl) has increased in recent years, its potential as a record of magmatic CO2contents remains untapped. We present the results of high-temperature, high-pressure experiments investigating the partitioning behaviour of CO2 between apatite and basaltic melt. Experiments were run in piston cylinder apparatus at 1 GPa and 1250 °C, with a slow initial cooling ramp employed to facilitate crystal growth. Each charge contained the starting basaltic powder doped with Ca-phosphate and variable proportions of H2O, CO2, and F. Run products are glass-rich charges containing 15-25 vol% large, euhedral apatite crystals (± cpx and minor biotite). Experimental apatites and glasses have been characterised by BSE imaging, electron microprobe, and ion microprobe. Apatites range in composition from near-endmember fluorapatite (3.0 wt% F), to near-endmember hydroxyapatite (1.7 wt% H2O), to carbon-rich apatite containing up to 1.6 wt% CO2. Apatite compositions are stoichiometric if all anions (F-, OH-, and CO32—) lie in the channel site, suggesting an "A-type" substitution under these conditions (i.e. CO32— + [] = 2X—, where X is another channel anion and [] is a vacancy; e.g. Fleet et al. 2004). Importantly, CO2 partitions readily into apatite at all fluid compositions considered here. CO2 is also more compatible in apatite than water at our run conditions, with calculated H2O-CO2 exchange coefficients close to or greater than 1. Our results indicate that when channel ions are primarily occupied by H2O and CO2 (i.e. F- and Cl-poor magmatic systems

Regardless of the thermal spraying system, a coating can only be as good as the quality of the input powders. Powder quality in turn is dependent on the manufacturing process and conditions. Thus, it is possible to alter characteristics such as morphology, porosity, phase composition, and the mechanical strength of the individual particles. This article looks at powder agglomerations using the spray drying technique. Two different spray drying configurations were used to produce spherical apatite powders. Apatite powders could be produced with variable densities. Rotary-atomized powders possessed internal porosity as well as open porosity. More applicable for thermal spraying are the nozzle-atomized powders, which are more dense. The particle size range produced is dependent on the many parameters in the spray drying process. Hydroxyapatite is more sensitive than fluorapatite to alterations in process conditions. The powders produced were clean, free of other phases, and possessed good flowability for thermal spraying purposes.

Moghaddam H.Y., Leventouri Th.* (Dept. of Physics & Alloy Research Center, Florida Atlantic Univ.) Chakoumakos B.C. (Solid State Division, Oak Ridge National Lab.**,kou@ornl.gov) We report Rietveld structural refinements of neutron diffraction data of a highly crystalline, single-phase natural carbonate apatite,(francolite of Epirus, Greece), in order to elucidate the details of carbonate substitution in the apatites. The composition is Ca9.56Na0.38Mg0.08(PO4)4.82(CO3)0.946(SO4)0.2F2.34, as determined by electron microprobe analysis. We report refinements of data for the native francolite as a function of temperature between 296K and 10K after the material had been heated at 750 °C to drive off adsorbed water and CO2. The neutron diffractioii@data were collected using a wavelength 1.0912 A on the HB4 high resolution powder diffractometer at the High Flux Isotope Reactor at Oak Ridge National Laboratory. Analysis of the temperature dependence of the anisotropic displacement parameters can reveal the contribution from the temperature independent static positional disorder. Difference displacement parameters evaluated along various bonding directions are being used to describe the mechanics and dynamics of the carbonate for phosphate substitution.*Supported by a SURA-ORNL Summer Cooperative Research Program 1998.**Supported by the Division of Materials Sciences,U.S. D.O.E. (contract DE-AC05-96OR22464 with Lockheed Martin Energy Research Corporation).

Available in abstract form only. Full text of publication follows: The goal of this study was to evaluate the effectiveness of Serbian natural mineral apatite as soil additive for reducing the migration of uranium from contaminated sediments. In laboratory study we investigated the sorption properties of domestic apatite upon different experimental conditions, such as pH, adsorbent mass, reaction period, concentration of P{sub 2}O{sub 5} in apatite, solid/liquid ratio. In second part of study, we did the quantification of uranium in soil samples, taken from uranium mine site 'Kalna', by sequential extraction method. The same procedure was, also, used for uranium determination in contaminated soil samples after apatite addition, in order to determine the changes in U distribution in soil fraction. The obtained results showed the significant level of immobilization (96.7%) upon certain conditions. Increase of %P{sub 2}O{sub 5} in apatite and process of mechano-chemical activation led to increase of immobilization capacity from 17.50% till 91.64%. The best results for uranium binding were obtained at pH 5.5 and reaction period 60 days (98.04%) The sequential extraction showed the presence of uranium (48.2%) in potentially available soil fractions, but with the apatite addition uranium content in these fractions decreased (30.64%), what is considering environmental aspect significant fact. In situ immobilization of radionuclide using inexpensive sequestering agents, such as apatite, is very adequate for big contaminated areas of soil with low level of contamination. This investigation study on natural apatite from deposit 'Lisina' Serbia was the first one of this type in our country. Key words: apatite, uranium, immobilization, soil, contamination. (authors)

Background Although biomimetic apatite coating is a promising way to provide titanium with osteoconductivity, the efficiency and quality of deposition is often poor. Most titanium implants have microscale surface morphology, and an addition of nanoscale features while preserving the micromorphology may provide further biological benefit. Here, we examined the effect of ultraviolet (UV) light treatment of titanium, or photofunctionalization, on the efficacy of biomimetic apatite deposition on titanium and its biological capability. Methods and results Micro-roughed titanium disks were prepared by acid-etching with sulfuric acid. Micro-roughened disks with or without photofunctionalization (20-minute exposure to UV light) were immersed in simulated body fluid (SBF) for 1 or 5 days. Photofunctionalized titanium disks were superhydrophilic and did not form surface air bubbles when immersed in SBF, whereas non-photofunctionalized disks were hydrophobic and largely covered with air bubbles during immersion. An apatite-related signal was observed by X-ray diffraction on photofunctionalized titanium after 1 day of SBF immersion, which was equivalent to the one observed after 5 days of immersion of control titanium. Scanning electron microscopy revealed nodular apatite deposition in the valleys and at the inclines of micro-roughened structures without affecting the existing micro-configuration. Micro-roughened titanium and apatite-deposited titanium surfaces had similar roughness values. The attachment, spreading, settling, proliferation, and alkaline phosphate activity of bone marrow-derived osteoblasts were promoted on apatite-coated titanium with photofunctionalization. Conclusion UV-photofunctionalization of titanium enabled faster deposition of nanoscale biomimetic apatite, resulting in the improved biological capability compared to the similarly prepared apatite-deposited titanium without photofunctionalization. Photofunctionalization-assisted biomimetic apatite

Biological apatite is an inorganic calcium phosphate salt in apatite form and nano size with a biological derivation. It is also the main inorganic component of biological hard tissues such as bones and teeth of vertebrates. Consequently, biological apatite has a wide application in dentistry and orthopedics by using as dental fillers and bone substitutes for bone reconstruction and regeneration. Given this, it is of great significance to obtain a comprehensive understanding of its physiochemical and biological properties. However, upon the previous studies, inconsistent and inadequate data of such basic properties as the morphology, crystal size, chemical compositions, and solubility of biological apatite were reported. This may be ascribed to the differences in the source of raw materials that biological apatite are made from, as well as the effect of the preparation approaches. Hence, this paper is to provide some insights rather than a thorough review of the physiochemical properties as well as the advantages and drawbacks of various preparation methods of biological apatite. PMID:24078928

All vertebrate skeletons are stiffened with apatite, a calcium phosphate mineral. Control of apatite mineralization is essential to the growth and repair of the biology of these skeletons, ensuring that apatite is deposited in the correct tissue location at the desired time. The mechanism of this biochemical control remains debated, but must involve increasing the localized apatite saturation state. It was theorized in 1923 that alkaline phosphatase (ALP) activity provides this control mechanism by increasing the inorganic phosphate (Pi) concentration via dephosphorylation of phosphorylated molecules. The ALP substrate for biological apatite is not known. We propose that polyphosphates (polyPs) produced by mitochondria may be the substrate for biological apatite formation by ALP activity. PolyPs (PO3-)n, also known as condensed phosphates, represent a concentrated, bioavailable Pi-storage strategy. Mitochondria import Pi and synthesize phosphate polymers through an unknown biochemical mechanism. When chelated with calcium and/or other cations, the effective P-concentration of these neutrally charged, amorphous, polyP species can be very high (~ 0.5 M), without inducing phosphate mineral crystallization. This P-concentration in the low Pi-concentration biological environment offers a method of concentrating P well above an apatite supersaturation required for nucleation. Bone is the most studied mineralized skeletal tissue. However, locating and analyzing active mineralizing areas is challenging. We studied calcified cartilage skeletons of elasmobranch fishes (sharks, stingrays and relatives) to analyse the phosphate chemistry in this continually mineralizing skeleton. Although the majority of the elasmobranch skeleton is unmineralized cartilage, it is wrapped in an outer layer of mineralized tissue comprised of small tiles called tesserae. These calcified tesserae continually grow through the formation of new mineral on their borders. Co-localization of ALP and

The recovery of phosphorus from incinerated sewage sludge ash (SSA) is assumed to be economical. Transformation from non-apatite inorganic phosphorus (NAIP) to apatite phosphorus (AP), which has a higher bioavailability and more extensive industrial applications, was studied at 750-950°C by sewage sludge incineration and model compound incineration with a calcium oxide (CaO) additive. Thermogravimetric differential scanning calorimetry analysis and X-ray diffraction measurements were used to analyze the reactions between NAIP with CaO and crystallized phases in SSA. High temperatures stimulated the volatilization of NAIP instead of AP. Sewage sludge incineration with CaO transformed NAIP into AP, and the percentage of AP from the total phosphorus reached 99% at 950°C. Aluminum phosphate reacted with CaO, forming Ca2P2O7 and Ca3(PO4)2 at 750-950°C. Reactions between iron phosphate and CaO occurred at lower temperatures, forming Ca(PO3)2 before reaching 850°C. PMID:26113414

The strength of granular sludge is essential for the mechanical stability of the granules. Inorganic precipitants form a major factor influencing the strength of the granules. To check the possibility of apatite accumulation in anammox granules, and study its contribution to the mechanical strength of granules, anammox granular sludge was collected from Dokhaven municipal wastewater treatment plant, the Netherlands. Mineral precipitation inside the granules was visualized by micro-computed tomography, and apatite was identified by electron probe microanalysis and X-ray powder diffraction. The mechanical strength of anammox granules was measured by a low load compression tester. The contribution of apatite to the mechanical strength was evaluated by the generalized Maxwell model. Ca-PO4 minerals are reported to accumulate in anammox granules. A transformation of Ca-PO4 happens, and apatite is the final stable form. The accumulation of apatite increases the mechanical strength of anammox granules. A fast method to monitor and evaluate the accumulation of minerals in anammox granules was proposed. PMID:23764605

Abutment and root portion divided two-piece dental implants were designed to modify the one-piece dense hydroxyapatite (D-HAP) implant. The initial placement of the root portion endosseously ensured an aseptic environment and physical stability for the implant during the bone healing period. The outer D-HAP shell of the root portion was fortified by an inner titanium cylinder and cemented with an adhesive resin cement containing 4-methacryloyoxyethyl trimellitate anhydride (4-META) and reinforced by fine apatite filler. Upon attaining integration of the bone and implant, the abutment was screwed and fixed into the screw hole of the root portion. The tissue response of both the apatite-filled resin cement and root portion of the two-piece implant was studied by animal canine experiments. Light and electron microscopic examination of specimens taken from experimental animal tissue showed bone contacted directly not only the exposed apatite filler at the surface of the apatite-filled resin cement, but also the resin portion. These findings of direct bone contact suggested that the tissue response of apatite-filled resin cement was approximately similar to the usual D-HAP. Because most of the surface of the outer D-HAP shell of the root portion came in contact with bone, it prevented the deposition of contamination on the D-HAP surface during the manufacturing procedures of the root portion. PMID:10148567

Biomimetic apatites are appealing compounds for the elaboration of bioactive bone-repair scaffolds due to their intrinsic similarity to bone mineral. Bone surgeries are however often heavy procedures, and the infiltration of pathogens may not be totally avoided. To prevent their development, systemic antibiotic prophylaxis is widespread but does not specifically target surgical sites and involves doses not always optimized. A relevant alternative is a preliminary functionalization by an infection-fighting agent. In this work, we investigated from a physicochemical viewpoint the association of a wide-spectrum antibiotic, tetracycline (TC), and a biomimetic nanocrystalline apatite previously characterized. TC adsorption kinetics and isotherm were thoroughly explored. Kinetic data were fitted to various models (pseudo-first-order, pseudo-second-order, general kinetic model of order n, Elovich, double-exponential, and purely diffusive models). The best fit was found for a double-exponential kinetic model or with a decimal reaction order of 1.4, highlighting a complex process with such TC molecules which do not expose high-affinity end groups for the surface of apatite. The adsorption isotherm was perfectly fitted to the Sips (Langmuir-Freundlich) model, while other models failed to describe it, and the Sips exponent greater than unity (1.08) suggested a joint impact of surface heterogeneity and positive cooperativity between adsorbed molecules. Finally, preliminary insights on TC release from pelletized nanocrystalline apatite, in aqueous medium and neutral pH, were obtained using a recirculation cell, indicating a release profile mainly following a Higuchi-like diffusion-limited rate. This work is intended to shed more light on the interaction between polar molecules not exhibiting high-affinity end groups and biomimetic apatites and is a starting point in view of the elaboration of biomimetic apatite-based bone scaffolds functionalized with polar organic drugs for a

In this study, the physicochemical properties and biocompatibilities of La-containing apatites were intensively investigated together with their characterizations in terms of composition, structure, valent state and morphology using X-ray diffraction, Fourier-transform infrared spectra, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively. The results indicate that the La(3+) ion can be incorporated into the crystal lattice of hydroxyapatite resulting in the production of La-incorporated apatites (La(x)Ca(10-x)(PO(4))(6)(OH)(2+x-2y)O(y square y-x) (x> or =0.5, y<1+x/2) or La(x)Ca(10-x)(PO(4))(6)O(y square y-x) (0.5apatites. In contrast to La-free apatite, La-incorporated apatites possess a series of attractive properties, including higher thermal stability, higher flexural strength, lower dissolution rate, larger alkaline phosphatase activity, preferable osteoblast morphology and comparable cytotoxicity. In particular, the sintered La-incorporated apatite block achieves a maximal flexure strength of 66.69+/-0.98 MPa at 5% La content (confidence coefficient 0.95), increased 320% in comparison with the La-free apatite. The present study suggests that the La-incorporated apatite possesses application potential in developing a new type of bioactive coating material for metal implants and also as a promising La carrier for further exploring the beneficial functions of La in the human body. PMID:19477306

Apatite is a common accessory mineral, and OH in apatite can indicate the fluid conditions of crystal formation. Previously, water (OH) concentration in apatite has often been estimated through electron microprobe analyses combined with mineral stoichiometry. However, the detection limit, precision, and accuracy of this method are not high. In this work, we calibrated the infrared spectroscopy (IR) method for measurement of OH concentration in apatite by using elastic recoil detection (ERD) analysis to obtain the absolute OH concentration. Large apatite wafers were cut perpendicular to the c-axis of each crystal and doubly polished. ERD measurements were carried out in the Michigan Ion Beam Laboratory at the University of Michigan to determine the hydrogen concentration in each sample. Each ERD spectrum was fitted and a hydrogen standard was used to quantify the hydrogen concentrations. Polarized transmission IR was used on apatite sections that were cut parallel to the c-axis, and doubly polished. IR measurements were made for E-vector parallel to the c-axis. Because the OH peak is intense, very thin samples must be used to avoid absorbance saturation; the thinnest sample (corresponding to the highest OH content) used was 17 µm thick. Four different apatite crystals were successfully analyzed using both the IR and ERD methods. Two were from Durango, Mexico; one from Imilchil, High Atlas Mountains, Morocco; and one from an unknown locality, purchased online from gem dealers. The OH peak near 3550 cm-1 was a relatively simple peak in all four samples. Therefore peak height was used for the absorbance value, A. Using the Beer-Lambert Law, a calibration line was established (R2= 0.95, for IR aperture of 50 µm x 50 µm) where the weight % of H2O is 0.013 times A/d, where d is the thickness in mm. The detection limit of H2O concentration in apatite by IR approaches ppm level for 0.1 mm wafers, the precision is better than 1% relative (depending on H2O content), and

Natural apatite samples with different F/Cl content from a variety of geological locations (Durango, Mexico; Mud Tank, Australia; and Snarum, Norway) were irradiated with swift heavy ions to simulate fission tracks. The annealing kinetics of the resulting ion tracks was investigated using synchrotron-based small-angle X-ray scattering (SAXS) combined with ex situ annealing. The activation energies for track recrystallization were extracted and consistent with previous studies using track-etching, tracks in the chlorine-rich Snarum apatite are more resistant to annealing than in the other compositions.

Carbon and oxygen isotopes were analyzed in carbonate apatite CO/sub 2/ and in co-existing calcite. Both C and O in apatite CO/sub 2/ are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure.

Hydroxyapatite (HAp) has been widely used as a biomaterial for substituting human hard tissues such as bone. By altering the morphology of HAp crystals, novel properties may be produced by controlling the orientation of the crystal planes. Apatite fibres were successfully synthesized by precipitation from aqueous solutions containing Ca(NO(3))(2), (NH(4))(2)HPO(4), urea and HNO(3). The products were composed of carbonate-containing apatite fibres with preferred orientation along the {h00} planes. Examination of individual fibres using transmission electron microscopy showed that the as-synthesized apatite fibres were highly strained single crystals with the c-axis orientation parallel to the long axis of the fibre. The crushed fibres consisted of domains that were preferentially oriented with the c-axis parallel to the long axis of the fibres. When the apatite fibres were heated to 800, 1000 and 1200 degrees C for 1h, the domains were removed and grain boundaries, dislocations and voids were formed. PMID:15621231

Apatite is a common accessory mineral in most rocks. A variety of trace elements can be substituted into apatite, meaning that apatite has the potential to record changes in the chemistry of ore-forming hydrothermal fluids. This study focuses on variations in apatite texture and chemistry around the world-class Carlin-type Au deposits of NE Nevada. These deposits are characterized by cryptic alteration of calcareous and siliciclastic sedimentary rocks induced by acidic, low-temperature (150-220 °C) ore fluids. A large database of apatite fission track (AFT) samples collected from NE Nevada (Hickey, unpublished data) is being used to examine relationships between apatite fission track ages, textural zonation within apatite crystals and apatite trace element composition. AFT data from "background" samples collected away from hydrothermal mineralization and Cenozoic igneous stocks reveal that regional uplift occurred in the Cretaceous at ~70-60 Ma. In comparison, AFT data from samples around gold mineralization reveal an Eocene heating event, interpreted as the result of hydrothermal reheating by the Carlin Au-forming system (Cline et al., 2005). Optical cathodoluminescence observations reveal that some apatite from Au-bearing material (Eocene AFT age) has embayed cores, and at least four generations of overgrowths (typically ˜10 μm wide overgrowths), which may also be embayed. In comparison, apatite from hydrothermally altered, but unmineralized, material has a single overgrowth generation. 'Background' apatites do not have significant overgrowths. Current research is characterizing the trace element composition of apatite cores and overgrowths via SIMS. We propose that apatite textures and trace element composition record hydrothermal fluid interactions. Applications include using apatite to detect the signature of hydrothermal fluids in rocks cryptically altered by low-temperature hydrothermal systems, or detecting mineralization by examining detrital apatites

The oxidation states of magmas provide valuable information about the release and speciation of volatile elements during volcanic eruptions, metallogenesis, source rock compositions, open system magmatic processes, tectonic settings and potentially titanium (Ti) activity in chemical systems used for Ti-dependent geothermometers and geobarometers. In this presentation we explore the use of Mn in apatite as an oxybarometer in intermediate and silicic igneous rocks. Increased Mn concentrations in apatite in granitic rocks from the zoned Criffell granitic pluton (southern Scotland) correlate with decreasing Fe2O3 (Fe3+) and Mn in the whole-rock and likely reflect increased Mn2+/Mn3+and greater compatibility of Mn2+ relative to Mn3+ in apatite under reduced conditions. Fe3+/Fe2+ ratios in biotites have previously been used to calculate oxygen fugacities (fO2) in the outer zone granodiorites and inner zone granites where redox conditions have been shown to change from close to the magnetite-hematite buffer to close to the nickel-nickel oxide buffer respectively[1]. This trend is apparent in apatite Mn concentrations from a range of intermediate to silicic volcanic rocks that exhibit varying redox states and are shown to vary linearly and negatively with log fO2, such that logfO2=-0.0022(±0.0003)Mn(ppm)-9.75(±0.46) Variations in the Mn concentration of apatites appear to be largely independent of differences in the Mn concentration of the melt. Apatite Mn concentrations may therefore provide an independent oxybarometer that is amenable to experimental calibration, with major relevance to studies on detrital mineral suites, particularly those containing a record of early Earth redox conditions, and on the climatic impact of historic volcanic eruptions[2]. [1] Stephens, W. E., Whitley, J. E., Thirlwall, M. F. and Halliday, A. N. (1985) The Criffell zoned pluton: correlated behaviour of rare earth element abundances with isotopic systems. Contributions to Mineralogy and

Titanium and its alloys are used as biomaterials, because of their high biocompatibility. Apatite precipitates on a titania surface in vivo, and living bone and titanium alloy are coupled through the thin apatite layer. The initial precipitation behavior of apatite on titania in simulated body fluid (SBF) solutions was evaluated and the effect of inorganic ions in the SBF was investigated. Measurement using the SPR phenomenon was used to evaluate the initial apatite precipitation. An SBF containing approximately equal ion concentrations to those in blood plasma was added to a titania surface and the SPR profile was obtained, from which the initial apatite precipitation rate was found to be 1.14 nm/h. Furthermore, the relationship between the inorganic concentration and the precipitation rate was determined for SBFs with different Na+ and Ca2+ concentrations. Apatite precipitation did not occur in the SBF with a low Na+ concentration, whereas the initial apatite precipitation rate in the SBF that did not contain Ca2+ was 0.32 nm/h. According to these results, Ca2+ has little effect on the initial apatite precipitation. In the initial reaction of apatite precipitation, sodium titanate is formed by the absorption of Na+. Next, calcium titanate precipitates upon the substitution of Na+ with Ca2+. Finally, Na+, phosphate ions and hydroxyl ions are attracted to the surface and apatite is formed. Thus, the rate-limiting factor in the initial nucleation of apatite is the Na+ concentration.

It is important to establish a thermodynamic data base for accessory minerals and mineral series that are useful in determining fluid composition during petrologic processes. As a starting point for apatite-system thermodynamics, Hovis and Harlov (2010, American Mineralogist 95, 946-952) reported enthalpies of mixing for a F-Cl apatite series. Harlov synthesized all such crystalline solutions at the GFZ-Potsdam using a slow-cooled molten-flux method. In order to expand thermodynamic characterization of the F-Cl-OH apatite system, a new study has been initiated along the F-OH apatite binary. Synthesis of this new series made use of National Institute of Standards and Technology (NIST) 2910a hydroxylapatite, a standard reference material made at NIST "by solution reaction of calcium hydroxide with phosphoric acid." Synthesis efforts at Lafayette College have been successful in producing fluorapatite through ion exchange between hydroxylapatite 2910a and fluorite. In these experiments, a thin layer of hydroxylapatite powder was placed on a polished CaF2 disc (obtained from a supplier of high-purity crystals for spectroscopy), pressed firmly against the disc, then annealed at 750 °C (1 bar) for three days. Longer annealing times did not produce further change in unit-cell dimensions of the resulting fluorapatite, but it is uncertain at this time whether this procedure produces a pure-F end member (chemical analyses to be performed in the near future). It is clear from the unit-cell dimensions, however, that the newly synthesized apatite contains a high percentage of fluorine, probably greater than 90 mol % F. Intermediate compositions for a F-OH apatite series were made by combining 2910a hydroxylapatite powder with the newly synthesized fluorapatite in various proportions, then conducting chemical homogenization experiments at 750 °C on each mixture. X-ray powder diffraction data indicated that these experiments were successful in producing chemically homogeneous

Dental implant failure often occurs due to oral bacterial infection. The aim of this study was to demonstrate that antibiotic efficacy could be enhanced with modified titanium. First, the titanium was modified by anodization and heat-treatment. Then, a biomimetic coating process was completed in two steps. Surface characterization was performed with scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Release of antibiotic was evaluated by UV/VIS spectrometry, and the antibacterial effect was evaluated on Streptococcus mutans. After the second coating step, we observed a thick homogeneous apatite layer that contained the antibiotic, cefalotin. The titanium formed a rutile phase after the heat treatment, and a carbonated apatite phase appeared after biomimetic coating. We found that the modified titanium increased the loading of cefalotin onto the hydroxyapatite coated surface. The results suggested that modified titanium coated with a cefalotin using biomimetic coating method might be useful for preventing local post-surgical implant infections. PMID:22277612

We have applied nonresonant laser secondary neutral mass spectrometry (Laser-SNMS) to examine different states of biomineralization in vitro. Primary osteoblast-like cells derived from bovine metacarpals were cultured for 5 weeks on clean smooth silicon substrates. For mass spectrometric investigations, the cells and newly formed mineral were cryofixed, freeze-fractured, and freeze-dried. The results indicate that in the vicinity of single osteoblasts, extracellular enrichment of potassium typically occurs during the initial stages of mineralization. Potassium may interact with matrix macromolecules and prevent an uncontrolled apatite deposition. However, apatite biomineral formation is correlated with a potassium release. In conclusion, potassium seems to be involved in the process of extracellular matrix biomineralization.

Methods for in situ formation in soil of a permeable reactive barrier or zone comprising a phosphate precipitate, such as apatite or hydroxyapatite, which is capable of selectively trapping and removing radionuclides and heavy metal contaminants from the soil, while allowing water or other compounds to pass through. A preparation of a phosphate reagent and a chelated calcium reagent is mixed aboveground and injected into the soil. Subsequently, the chelated calcium reagent biodegrades and slowly releases free calcium. The free calcium reacts with the phosphate reagent to form a phosphate precipitate. Under the proper chemical conditions, apatite or hydroxyapatite can form. Radionuclide and heavy metal contaminants, including lead, strontium, lanthanides, and uranium are then selectively sequestered by sorbing them onto the phosphate precipitate. A reducing agent can be added for reduction and selective sequestration of technetium or selenium contaminants.

Two series of strontium-lanthanum apatites, Sr{sub 10-x}La {sub x}(PO{sub 4}){sub 6-x}(SiO{sub 4}) {sub x}F{sub 2} and Sr{sub 10-x}La {sub x}(PO{sub 4}){sub 6-x}(SiO{sub 4}) {sub x}O with 0 {<=} x {<=} 6, were synthesized by solid state reaction in the temperature range of 1200-1400 deg. C. The obtained materials were characterized by powder X-ray diffraction, infrared absorption spectroscopy and solid {sup 31}P Nuclear Magnetic Resonance. Pure solid solutions were obtained within a limited range of unsubstituted phosphate and silicate apatites. A variation of the lattice parameters was observed, with an increase of a and a decrease of c parameters, related to the radius of the corresponding substituted ions.

Thirty-four apatite fission-track apparent ages and twenty-four track length distributions for ash bed samples from the Valley and Ridge Province and Upper Devonian to Upper Pennsylvania sedimentary samples from the Allegheny Front and Allegheny Plateau of Pennsylvania suggest that these regions represent different thermal (uplift) regimes as well as different structural provinces. The Valley and Ridge Province Tioga and Kalkberg ash bed samples yield apatite fission-track apparent ages and track length distributions that indicate early post-Alleghanian (285-270 Ma) cooling and unroofing that began at ˜250 Ma. Assuming a geothermal gradient of 25°C km -1, a burial depth of at least 3.4 km can be estimated for all the Pennsylvania samples. At the Allegheny structural front and on the western Allegheny Plateau, the apatite fission-track apparent ages (<150 Ma) and track length measurements indicate a Late Jurassic-Early Cretaceous thermal event for these samples possibly resulting from a higher geothermal gradient coinciding with kimberlite intrusion at this time along the Greene-Potter Fault Zone. In northeast Pennsylvania on the Allegheny Plateau, the Upper Paleozoic sedimentary samples yield apatite fission-track apparent ages ≤180 Ma. Narrow track length distributions with long mean lengths (13-14 μm) and small standard deviations (1.3 μm) suggest rapid cooling from temperatures >110°C during the Middle Jurassic-Early Cretaceous for this part of Pennsylvania. This is consistent with the suggested uplift history of the Catskill Mountain region in adjacent New York State.

Alkaline-heat-treated titanium self-forms an apatite surface layer in vivo. The aim of the present study was to materialistically characterize the surface of alkaline-heat-treated titanium immersed in simulated body fluid (AHS-TI) and to examine the differentiation behavior of osteoblasts on AHS-TI. SEM, thin-film XRD, FTIR, and XPS analyses revealed that AHS-TI contained a 1.0- micro m-thick, low-crystalline, and [002] direction-oriented carbonate apatite surface. Human osteoblast-like SaOS-2 cells were cultured on polystyrene, titanium, and AHS-TI, and RT-PCR analyses of osteogenic differentiation-related mRNAs were conducted. On AHS-TI, the expression of bone sialoprotein mRNA was up-regulated as compared with that on polystyrene and titanium (p < 0.05). On AHS-TI, the expression of osteopontin and osteocalcin mRNAs was up-regulated as compared with that on polystyrene (p<0.05). The results indicate that the apatite was bone-like and accelerated the osteogenic differentiation of SaOS-2, suggesting that alkaline-heat treatment might facilitate better integration of titanium implants with bone. PMID:15153453

There is continuing debate about whether abundant citrate plays an active role in biomineralization of bone. Using solid state NMR dipolar dephasing, we examined another normally mineralized hard tissue, mineralized articular cartilage, as well as biocalcifications arising in pathological conditions, mineralized intimal atherosclerotic vascular plaque, and apatitic uroliths (urinary stones). Residual nondephasing ¹³C NMR signal at 76 ppm in the spectra of mineralized cartilage and vascular plaque indicates that a quaternary carbon atom resonates at this frequency, consistent with the presence of citrate. The presence, and as yet unproven possible mechanistic involvement, of citrate in tissue mineralization extends the compositional, structural, biogenetic, and cytological similarities between these tissues and bone itself. Out of 10 apatitic kidney stones, five contained NMR-detectable citrate. Finding citrate in a high proportion of uroliths may be significant in view of the use of citrate in urolithiasis therapy and prophylaxis. Citrate may be essential for normal biomineralization (e.g., of cartilage), play a modulatory role in vascular calcification which could be a target for therapeutic intervention, and drive the formation of apatitic rather than other calcific uroliths, including more therapeutically intractable forms of calcium phosphate. PMID:23780351

Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10-100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite. ?? 1986 Springer-Verlag.

We have conducted a computational study to investigate a number of possible routes for the incorporation of carbon into apatites. Using density functional theory (DFT) we have calculated geometry optimised structures for fluor- and hydroxy-apatites with and without various substitutions. We have studied several different carbonate substitutions, pure carbonate and pure formate apatites, neutral carbon atoms occupying interstices, and carbon dioxide and acetylene absorbed in oxyapatite.

Apatites of hard tissues of teeth of persons of different sex and age were studied in detail. It is shown that the crystal structure of apatites depends on changes in the composition of the enamel that happen during a person's life. Limits of the variations of the crystal lattice parameters of the enamel apatites connected with the complicate processes of de- and remineralization have been determined. On the basis of the identified correlations between chemical composition, crystal lattice parameters and age of patients, the complicated interrelated isomorphic replacements occurring in the crystal structure of apatites of hard tooth tissues during aging were analysed. PMID:25946859

The mineral apatite is characterized by elevated and highly variable Lu/Hf ratios that, in some cases, allow for single-crystal dating by the Lu-Hf isotopic system. Apatites from the Adirondack Lowlands and Otter Lake area in the Grenville Province, and from the Black Hills, South Dakota, yield Lu-Hf ages that are consistently older than their respective Pb step leaching ages. Isotopic closure for the Lu-Hf system, therefore, occurs before U-Pb system closure in this mineral. In the Adirondack Lowlands, where H 2O activity was low, Lu-Hf systematics of cm-sized apatite crystals remained undisturbed during upper amphibolite facies metamorphism (˜700 to 675 °C) at 1170-1130 Ma. The relatively old Lu-Hf ages of 1270 and 1230 Ma observed for these apatites correlate with decreasing crystal size. In contrast, apatite from the fluid-rich Otter Lake area and Black Hills yields unrealistically low apparent Lu-Hf closure temperatures, implying that in these apatites, fluids facilitated late exchange. The Lu-Hf ages for the metamorphic apatites were thus controlled either by the prevailing temperature and grain size, or by fluid activity.

Understanding the crystal chemistry of nuclear waste forms is critical to proper evaluation of their potential use and stability. Because of apatite's ability to incorporate rare earth elements and actinides, there is great interest in it as a solid nuclear waste form and an engineered contaminant barrier. However, the crystal chemistry of actinides in the apatite structure is still poorly understood. Through the complementary use of single crystal X-ray diffraction and X-ray absorption spectroscopy, we present here the first direct results on the site occupancy of thorium in apatite structure and the structural distortion created by its substitution. Single crystal X-ray diffraction data were used to refine the structure and site occupancies of a synthetic fluorapatite with approximately 2 wt% Th in the structure. The structure refinements of three separate crystals with R = 0.0167-0.0217 indicate that Th substitutes almost extensively into the Ca2 site. The value of ThCa(2)/ThCa(1), calculated per individual site to account for the different multiplicity of the two Ca sites, is 6.5. X-ray absorption spectroscopy was used to probe the local structure of Th in this synthetic fluorapatite (single crystal form), as well as Th in a natural fluorapatite (powder form) from Mineville, NY with the Th concentration of approximately 2000 ppm. The results from extend X-ray absorption fine structure (EXAFS) also indicate that Th partitions into the Ca2 site and yields Th specific bond distances which are not obtainable from single crystal X-ray diffraction.

Chronic acid deposition has depleted calcium (Ca) from many New England forest soils, and intensive harvesting may reduce phosphorus (P) available to future rotations. Thin glacial till soils contain trace amounts of apatite, a primary calcium phosphate mineral, which may be an important long-term source of both P and Ca to ecosystems. The extent to which ECM fungi enhance the weathering rate of primary minerals in soil which contain growth-limiting nutrients remains poorly quantified, in part due to biogeochemical tracers which are subsequently masked by within-plant fractionation. Rare earth elements (REEs) and Pb isotope ratios show some potential for revealing differences in soil apatite weathering rates across forest stands and silvicultural treatments. To test the utility of these tracers, we grew birch seedlings semi-hydroponically under controlled P-limited conditions, supplemented with mesh bags containing granite chips. Our experimental design included nonmycorrhizal (NM) as well as ectomycorrhizal cultures (Cortinarius or Leccinum). Resulting mycorrhizal roots and leachates of granite chips were analyzed for these tracers. REE concentrations in roots were greatly elevated in treatments with granite relative to those without granite, demonstrating uptake of apatite weathering products. Roots with different mycorrhizal fungi accumulated similar concentrations of REEs and were generally elevated compared to the NM cultures. Ammonium chloride leaches of granite chips grown in contact with mycorrhizal hyphae show elevated REE concentrations and significantly radiogenic Pb isotope signatures relative to bulk rock, also supporting enhanced apatite dissolution. Our results in culture are consistent with data from field-collected sporocarps from hardwood stands in the Bartlett Experimental Forest in New Hampshire, in which Cortinarius sporocarp Pb isotope ratios were more radiogenic than those of other ectomycorrhizal sporocarps. Taken together, the experimental

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to estimates of Mars' bulk crust composition [1]. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the crustal composition of components that cannot be measured directly by remote sensing. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034.

Modification of organic polymer with silanol groups in combination with calcium salts enables the polymer to show bioactivity, that is, the polymer forms apatite on its surface after exposure to body environment. However, how modification with silanol groups influences ability of apatite formation on the polymer substrate and adhesive strength between polymer and apatite is not yet known. In the present study, polyamide containing carboxyl groups was modified with different amounts of silanol groups, and its apatite-forming ability in 1.5SBF, which contained ion concentrations 1.5 times those of simulated body fluid (SBF), was examined. The rate of apatite formation increased with increasing content of silanol groups in the polyamide films. This may be attributed to enhancement of dipole interactions. A tendency for the adhesive strength of the apatite layer on the polyamide film to be decreased with increasing content of silanol groups was observed. This may be attributed to swelling in 1.5SBF and having a high degree of shrinkage after drying. These findings clearly show that modification of organic polymers with the functional groups induces apatite deposition, and also determines the adhesive strength of the apatite layer to the organic substrates. PMID:17243002

ABSTRACT. In 2000, a reactive barrier was installed on the East Fork of Ninemile Creek near Wallace, Idaho to treat acid mine discharge. The barrier was filled with fishbone derived Apatite IITM to remove the contaminants of concern (Zn, Pb, and Cd) and raise the pH of the acidic mine discharge. Metal removal has been achieved by a combination of chemical, biological, and physical precipitation. Flow for the water ranges from 5 to 35 gallons per minute. The water is successfully being treated, but the system experienced varying degrees of plugging. In 2002, gravel was mixed with the Apatite IITM to help control plugging. In 2003 the Idaho National Laboratory was ask to provide technical support to the Coeur d’Alene Basin Commission to help identify a remedy to the plugging issue. Air sparging was employed to treat the plugging issues. Plastic packing rings were added in the fall of 2005, which have increased the void space in the media and increased flows during the 10 months of operation since the improvements were made.

The replacement of aragonite by apatite is a process that occurs naturally during diagenesis, chemical weathering and natural hydrothermal reactions and is artificially promoted in medical sciences for use of the product material as a bone implant. We have investigated the mechanism and the kinetics of this replacement by using biogenic aragonite (cuttlebone of the Sepia officinalis) as a starting material and reacting it with di-ammonium hydrogen phosphate solution. Isothermal experiments were carried out over a range of temperatures up to 190 °C. Quantification of each solid phase, for different reaction times, was obtained by the Rietveld analysis of powder X-ray diffraction patterns. An empirical activation energy was calculated by using two different approaches to analyze the data. Scanning electron microscopy showed that the fine structure of the cuttlebone was perfectly retained even after aragonite had been completely converted to apatite. We present a detailed investigation of the kinetics of a reaction that involves interaction of a solid phase with an aqueous fluid and leads to a pseudomorphic replacement of the initial solid phase by a new, chemically different, phase. This replacement process is described in terms of an interface-coupled dissolution-reprecipitation mechanism.

Several of the gamma-emitting U-Th series, cosmogenic and anthropogenic radionuclides (210Pb, 234Th, 226Ra, 228Ra, 7Be, 137Cs, etc) have been widely utilized as tracers and chronometers in environmental studies. Precise measurements of these nuclides using gamma-ray spectrometry in environmental matrices require that the proper correction factors for self- and external-absorption be applied. In this study, we examine factors associated with absorption and self attenuation of gamma-rays of 210Pb (46.5 keV), 234Th (63 keV), 226Ra (via 214Pb and 214Bi, 351.9 and 609 keV) and 228Ra (via 228Ac, 338.3 and 911.2 keV) using a well-type germanium gamma-ray detector. Samples of three naturally occurring minerals (titanite, apatite and zircon) were separated into 5 size fractions (<63 μm, 63-125 μm, 125-250 μm, 250-500 μm, and >500 μm) and analyzed for 210Pb, 234Th, 226Ra, and 228Ra. We also analyzed two synthetic silica standards (RGU-1, RGTH-1) that have a relatively uniform grain size of 63 μm. These minerals were chosen based on their varying chemical compositions and densities. Chosen samples are of an age that isotopes of 238U and 232Th are expected to be in secular equilibrium with their daughter products. However, the measured activity ratios between members of the family vary widely. In the case of titanite, the 210Pb/226Ra ratios in 5 size fractions varied between 0.44×0.03 and 0.53×0.03, while in apatite it varied between 0.54×0.03 and 0.67×0.04, without applying any self- and external-absorption correction factors. Using the attenuation coefficients of constituent elements at different energies, we estimate the attenuation coefficient for each of these 4 minerals and determine the self- and external-absorption correction factors. The self- and external-absorption corrected activities agree with the expected activities in these minerals. Our data suggests that variations in the activity levels are dependent on chemical composition, density, and grain

Abstract Aim: Calcium silicate cements are widely used in endodontics. Novel fast-setting calcium silicate cement with fluoride (Protooth) has been developed for potential applications in teeth crowns including cavity lining and cementation. Objective: To evaluate the surface apatite-forming ability of Protooth compositions as a function of fluoride content and immersion time in phosphate-buffered saline (PBS). Material and methods: Three cement compositions were tested: Protooth (3.5% fluoride and 10% radiocontrast), ultrafast Protooth (3.5% fluoride and 20% radiocontrast), and high fluoride Protooth (15% fluoride and 25% radiocontrast). Powders were cap-mixed with liquid, filled to the molds and immersed in PBS. Scanning electron microscopy, energy dispersive X-ray analysis, and Raman spectroscopy were used to characterize the precipitations morphology and composition after 1, 7, 28, and 56 days. Apatite/belite Raman peak height indicated the apatite thickness. Results: Spherical calcium phosphate precipitations with acicular crystallites were formed after 1-day immersion in PBS and Raman spectra disclosed the phosphate band at 965 cm−1, supporting the apatite formation over Protooth compositions. The apatite deposition continued and more voluminous precipitations were observed after 56 days over the surface of all cements. Raman bands suggested the formation of β-type carbonated apatite over Protooth compositions. High fluoride Protooth showed the most compact deposition with significantly higher apatite/belite ratio compared to Protooth and ultrafast Protooth after 28 and 56 days. Conclusions: Calcium phosphate precipitations (apatite) were formed over Protooth compositions after immersion in PBS with increasing apatite formation as a function of time. High fluoride Protooth exhibited thicker apatite deposition. PMID:27335901

Materials with apatite crystal structure provide a great potential for incorporating the long-lived radioactive iodine isotope (129I) in the form of iodide (I-) from nuclear waste streams. Because of its durability and potentially high iodine content, the apatite waste form can reduce iodine release rate and minimize the waste volume. Crystal structure and composition of apatite was investigated for iodide incorporation into the channel of the structure using Artificial Neural Network. A total of 86 experimentally determined apatite crystal structures of different compositions were compiled from literature, and 46 of them were used to train the networks and 42 were used to test the performance of the trained networks. The results show that the performances of the networks are satisfactory for predictions of unit cell parameters a and c and channel size of the structure. The trained and tested networks were then used to predict unknown compositions of apatite that incorporates iodide. With a crystal chemistry consideration, chemical compositions that lead to matching the size of the structural channel to the size of iodide were then predicted to be able to incorporate iodide in the structural channel. The calculations suggest that combinations of A site cations of Ag+, K+, Sr2+, Pb2+, Ba2+, and Cs+, and X site cations, mostly formed tetrahedron, of Mn5+, As5+, Cr5+, V5+, Mo5+, Si4+, Ge4+, and Re7+ are possible apatite compositions that are able to incorporate iodide. The charge balance of different apatite compositions can be achieved by multiple substitutions at a single site or coupled substitutions at both A and X sites. The results give important clues for designing experiments to synthesize new apatite compositions and also provide a fundamental understanding how iodide is incorporated in the apatite structure. This understanding can provide important insights for apatite waste forms design by optimizing the chemical composition and synthesis procedure.

At the time of publication of New Views of the Moon, it was thought that the Moon was bone dry with less than about 1 ppb H2O. However in 2007, initial reports at the 38th Lunar and Planetary Science Conference speculated that H-species were present in both apatites and pyroclastic volcanic lunar glasses. These early reports were later confirmed through peer-review, which motivated many subsequent studies on magmatic volatiles in and on the Moon within the last decade. Some of these studies have cast into question the post-Apollo view of lunar formation, the distribution and sources of volatiles in the Earth-Moon system, and the thermal and magmatic evolution of the Moon. The mineral apatite has been one of the pillars of this new field of study, and it will be the primary focus of this abstract. Although apatite has been used both to understand the abundances of volatiles in lunar systems as well as the isotopic compositions of those volatiles, the focus here will be on the abundances of F, Cl, and H2O. This work demonstrates the utility of apatite in advancing our understanding of lunar volatiles, hence apatite should be among the topics covered in the endogenous lunar volatile chapter in NVM II. Truncated ternary plot of apatite X-site occupancy (mol%) from highlands apatite and mare basalt apatite plotted on the relative volatile abundance diagram from. The solid black lines delineate fields of relative abundances of F, Cl, and H2O (on a weight basis) in the melt from which the apatite crystallized. The diagram was constructed using available apatite/melt partitioning data for fluorine, chlorine, and hydroxyl.

Appropriate setting time is an important parameter that determines the effectiveness of apatite cement (AC) for clinical application, given the issues of crystalline inflammatory response phenomena if AC fails to set. To this end, the present study analyzes the effects of the method of apatite seed crystals addition on the setting reaction of α-tricalcium phosphate (α-TCP) based AC. Two ACs, both consisting of α-TCP and calcium deficient hydroxyapatite (cdHAp), were analyzed in this study. In one AC, cdHAp was added externally to α-TCP and this AC was abbreviated as AC(EA). In the other AC, α-TCP was partially hydrolyzed to form cdHAp on the surface of α-TCP. This AC was referred to as AC(PH). Results indicate a decrease in the setting time of both ACs with the addition of cdHAp. Among them, for the given amount of added cdHAp, AC(PH) showed relatively shorter setting time than AC(EA). Besides, the mechanical strength of the set AC(PH) was also higher than that of set AC(EA). These properties of AC(PH) were attributed to the predominant crystal growth of cdHAp in the vicinity of the α-TCP particle surface. Accordingly, it can be concluded that the partial hydrolysis of α-TCP may be a better approach to add low crystalline cdHAp onto α-TCP based AC. PMID:26411440

Apatite (Ca5(PO4)3(OH, F, Cl)) is one of the main host of halogens in magmatic and metamorphic rocks and plays a unique role during fluid-rock interaction as it incorporates halogens (i.e. F, Cl, Br, I) and OH from hydrothermal fluids to form a ternary solid solution of the endmembers F-apatite, Cl-apatite and OH-apatite. Here, we present an experimental study to investigate the processes during interaction of Cl-apatite with different aqueous solutions (KOH, NaCl, NaF of different concentration also doped with NaBr, NaI) at crustal conditions (400-700 °C and 0.2 GPa) leading to the formation of new apatite. We use the experimental results to calculate partition coefficients of halogens between apatite and fluid. Due to a coupled dissolution-reprecipitation mechanism new apatite is always formed as a pseudomorphic replacement of Cl-apatite. Additionally, some experiments produce new apatite also as an epitaxial overgrowth. The composition of new apatite is mainly governed by complex characteristics of the fluid phase from which it is precipitating and depends on composition of the fluid, temperature and fluid to mineral ratio. Furthermore, replaced apatite shows a compositional zonation, which is attributed to a compositional evolution of the coexisting fluid in local equilibrium with the newly formed apatite. Apatite/fluid partition coefficients for F depend on the concentration of F in the fluid and increase from 75 at high concentrations (460 μg/g F) to 300 at low concentrations (46 μg/g F) indicating a high compatibility of F in apatite. A correlation of Cl-concentration in apatite with Cl- concentration of fluid is not observed for experiments with highly saline solutions, composition of new apatite is rather governed by OH- concentration of the hydrothermal fluid. Low partition coefficients were measured for the larger halogens Br and I and vary between 0.7 * 10-3-152 * 10-3 for Br and 0.3 * 10-3-17 * 10-3 for I, respectively. Br seems to have D values of

An assessment of F-C1-OH partitioning between natural apatite and biotite in a variety of rocks was used to evaluate reciprocal (Mg, Fe 2+, Al VI) (F, Cl, OH) mixing properties for biotite according to the reciprocal salt solution model of WOOD and NICHOLLS (1978). Ideal mixing of F-C1-OH and Fe-Mg-Al VI in the hydroxyl and octahedral sites is assumed for biotites with dilute Cl concentrations. The reciprocal interaction parameters, in terms of Gibbs free energies, for the reactions KMg3[ AlSi3O10]( OH) 2 + KFe3[ AlSi3O10]( F) 2 = KMg3[ AlSi3O10]( F) 2 + KFe3[ AlSi3O10]( OH) 2 Phl Fann Fphl Ann and KMg3[ AlSi3O10]( Cl) 2 + KFe3[ AlSi3O10]( OH) 2 = KMg3[ AlSi3O10]( OH) 2 + KFe3[ AlSi3O10] ( Cl) 2 Clphl Ann Phl Clann are about -10 kcal/mol and -4.5 kcal/mol, respectively. These mixing properties are consistent with standard state thermodynamic properties for F and Cl endmember phases from ZHU and SVERJENSKY (1991). The approach of studying F-C1-OH partitioning between biotite and apatite permits distinguishing the reciprocal effects from the effects of temperature, pressure, and fluid composition. The resultant mixing properties are consistent with observations both in hydrothermal experiments and in natural mineral assemblages. The mixing properties presented in this study enable us now to predict F and Cl concentrations of hydrothermal fluids from the measured F and Cl concentrations in biotite with variable Fe-Mg-Al VI proportions. A case study of the Santa Rita porphyry copper deposits, New Mexico, shows that hydrothermal fluids responsible for the phyllic alteration had a salinity about 3 molal Cl -, in agreement with fluid inclusion studies. Our internally consistent standard thermodynamic properties and solid solution models also lead to recalibration of the apatite-biotite geothermometer. The revised geothermometer predicts temperatures that agree with those estimated from other independent geothermometers. The large reciprocal effects in biotite also point

The iron oxide-hydroxyapatite (FeOxHA) nanoparticles reported here differ from those reported before by their advantage of homogeneity and simple preparation; moreover, the presence of carboxymethyldextran (CMD), together with hydroxyapatite (HA), allows access to the cellular membrane, which makes our magnetic apatite unique. These nanoparticles combine magnetic behavior, Raman label ability and the property of interaction with the cellular membrane; they therefore represent an interesting material for structural differentiation of the cell membrane. It was observed by Raman spectroscopy, scanning electron microscopy (SEM) and fluorescence microscopy that FeOxHA adheres to the plasma membrane and does not penetrate the membrane. These insights make the nanoparticles a promising material for magnetic cell sorting, e.g. in microfluidic device applications.

Life support systems at a lunar or martian outpost will require the ability to produce food growing in 1) treated lunar or martian regolith; 2) a synthetic soil, or 3) some combination of both. Zeoponic soil, composed of NH4 (-) and K-exchanged clinoptilolite (Cp) and synthetic apatite (Ap), can provide slow-release fertilization via dissolution and ion-exchange. Equilibrium studies indicate that KNH4, P, and Mg are available to plants at sufficient levels, however, Ca is deficient. Ca availability can be increased by adding a second Ca-bearing mineral: calcite (Cal); dolomite (Dol); or wollastonite (Wol). Additions of Cal, Dol, and Wol systematically change the concentrations of Ca and P in solution. Cal has the greatest effect, Dol the least, and Wol is intermediate.

Halogen composition of replaced apatite formed during a regional metasomatic event (Bamble Sector, SE Norway) reveals information about the composition and evolution of the hydrothermal fluid. Infiltration and pervasive fluid flow of highly saline fluids into gabbroic bodies lead to scapolitization and amphibolitization, where magmatic Cl-rich apatite reacts with the hydrothermal fluid to form OH- and/or F-rich apatite. Apatite from highly altered samples adjacent to the shear zone has highest F (up to 15,000 µg/g) and lowest Br (4-25 µg/g) concentrations, whereas apatite from least altered samples has very low F (30-200 µg/g) and high Br (30-85 µg/g). In addition, individual replaced apatite grains show a zonation in F with high concentrations along rims and cracks and low F in core regions. Iodine concentrations remain rather constant as low values of 0.18-0.70 µg/g. We interpret all observed compositional features of replaced apatite to be the result of a continuous evolution of the fluid during fluid-rock interaction. Due to its high compatibility, F from the infiltrating fluid is incorporated early into recrystallized apatite (close to shear zone and rims of individual apatite grains). In contrast, Br as an incompatible halogen becomes enriched in the fluid and is highest in the most evolved fluid. Using experimental partition data between replaced apatite and fluid, we calculated F concentrations of the evolving fluid to decrease from 60 to <1 µg/g and Br to increase from ~1200 to ~5000 µg/g; I concentrations of the fluid are constant in the order of 370 µg/g. Although Cl is expected to show a similar behavior as Br, replaced apatite has constant Cl concentrations throughout the alteration sequence (~1 wt.%), which is likely the result of a rather constant Cl activity in the fluid. Chlorine stable isotope values of individual apatite grains are heterogeneous and range from -1.2 to +3.7 ‰. High δ 37Cl values are generally correlated with OH

Vertically aligned one-dimensional hybrid structures, which are composed of apatite and graphitic structures, can be beneficial for orthopedic applications. However, they are difficult to generate using the current method. Here, we report the first synthesis of a single-crystal apatite nanowire encapsulated in graphitic shells by a one-step chemical vapor deposition. Incipient nucleation of apatite and its subsequent transformation to an oriented crystal are directed by derived gaseous phosphorine. Longitudinal growth of the oriented apatite crystal is achieved by a vapor-solid growth mechanism, whereas lateral growth is suppressed by the graphitic layers formed through arrangement of the derived aromatic hydrocarbon molecules. We show that this unusual combination of the apatite crystal and the graphitic shells can lead to an excellent osteogenic differentiation and bony fusion through a programmed smart behavior. For instance, the graphitic shells are degraded after the initial cell growth promoted by the graphitic nanostructures, and the cells continue proliferation on the bare apatite nanowires. Furthermore, a bending experiment indicates that such core-shell nanowires exhibited a superior bending stiffness compared to single-crystal apatite nanowires without graphitic shells. The results suggest a new strategy and direction for bone grafting materials with a highly controllable morphology and material conditions that can best stimulate bone cell differentiation and growth. PMID:23755838

Apatite was applied onto the fiber surface of an interbonded three-dimensional polycaprolactone fibrous scaffold through a vacuum nitrogen plasma pretreatment followed by immersion in a simulated body fluid. The plasma pretreatment improved the wettability and accelerated apatite deposition on the fiber surface. The apatite coating was proven to be biocompatible to fibroblast cells without any cytotoxicity. Two osteoblast cell lines, human fetal osteoblast cells (hFOB1.19) and human osteosarcoma cells (Saos-2), were used for evaluating the cell response of the fibrous matrices. The apatite coating showed enhanced cell attachment for both hFOB1.19 and Saos-2 cells. In comparison to the uncoated fibrous scaffolds, the apatite-coated fibrous matrix had an improved hFOB1.19 cell proliferation for at least 2 weeks. Enhanced cell differentiation was also observed on the apatite-coated fibrous matrix primarily on the third, 10th, and 14th days of culture. Saos-2 cells showed improved proliferation in the apatite-coated matrix mainly on days 3 and 14, but the differentiation was increased only on the third day of culture. PMID:22941867

A systematic study is made on the electronic structure of stoichiometric calcium and lead apatites, using the tight binding extended Hückel method (eHT). The aim is to investigate the applicability of the semiempirical theory to study this family of compounds. A10(BO4)6X2 (A = Ca, Pb) apatites, differing by substitutions in the BO4 tetrahedral unit (B = P, As, and V) and X-channel ion (X = OH, Cl), are considered. The calculations show that eHT is suitable to describe basic properties especially concerning trends with atomic substitution and geometry changes. Band structure, Mulliken charge distribution, and bond orders are in good agreement with results of ab initio density functional theory (DFT) found in the literature. Large variations in the optical gap due to vanadium and lead substitutions are newly found. Changes in the anion X-channel affect the optical gap, which is in close agreement with DFT results. Analysis involving subnets are performed to determine the role of halogenic orbitals in the electronic structure of chloroapatites, showing evidence of covalent Cl bonding. It was also found that Pb=OH bonding in hydroxy-vanadinite Pb10(VO4)6(OH)2, recently synthesized, is weaker than that of Ca=OH in vanadate Ca10(VO4)6(OH)2. Arsenium is found to be more weakely bound to the O-tetrahedron than phosphorous, although Ca=O bond is increased with the substitution. We investigate, in addition, the electronic structure of a model system Ca10(AsO4)6(OH)2, obtained from direct As substitution in the vanadate Ca10(VO4)6(OH)2.

The present work investigates the preparation of biomimetic nanocrystalline apatites co-substituted with Mg, CO3 and Sr to be used as starting materials for the development of nanostructured bio-devices for regeneration of osteoporotic bone. Biological-like amounts of Mg and CO3 ions were inserted in the apatite structure to mimic the composition of bone apatite, whereas the addition of increasing quantities of Sr ions, from 0 up to 12 wt.%, as anti-osteoporotic agent, was evaluated. The chemical-physical features, the morphology, the degradation rates, the ion release kinetics as well as the in vitro bioactivity of the as-prepared apatites were fully evaluated. The results indicated that the incorporation of 12 wt.% of Sr can be viewed as a threshold for the structural stability of Mg-CO3-apatite. Indeed, incorporation of lower quantity of Sr did not induce considerable variations in the chemical structure of Mg-CO3-apatite, while when the Sr doping extent reached 12 wt.%, a dramatically destabilizing effect was detected on the crystal structure thus yielding alteration of the symmetry and distortion of the PO4. As a consequence, this apatite exhibited the fastest degradation kinetic and the highest amount of Sr ions released when tested in physiological conditions. In this respect, the surface crystallization of new calcium phosphate phase when immersed in physiological-like solution occurred by different mechanisms and extents due to the different structural chemistry of the variously doped apatites. Nevertheless, all the apatites synthesized in this work exhibited in vitro bioactivity demonstrating their potential use to develop biomedical devices with anti-osteoporotic functionality. PMID:24411371

The particle size of apatite is one of the critical factors that influence the adsorption of heavy metals on apatite in the remediation of heavy metal contaminated soils using apatite. However, little research has been done evaluating the impact of different particle sizes of apatite on immobilization remediation of heavy metal polluted soils in field. In this study, the adsorption isothermal experiments of copper on three kinds of apatite was tested, and the field experiment by using different particle sizes apatite [nano-hydroxyapatite (NAP), micro-hydroxyapatite (MAP), ordinary particle apatite (OAP)] at a same dosage of 25.8 t/ha (1.16 %, W/W) was also conducted. Ryegrass was chosen as the test plant. The ryegrass biomass, the copper contents in ryegrass and the copper fractionations in soil were determined after field experiments. Results of adsorption experiments showed that the adsorption amounts of copper on OAP was the lowest among different particles. The adsorption amounts of copper on MAP was higher than NAP at high copper equilibrium concentration (>1 mmol L(-1)), an opposite trend was obtained at low copper concentration (<1 mmol L(-1)). In the field experiment, we found that the application of different apatites could effectively increase the soil pH, decrease the available copper concentration in soil, provide more nutrient phosphate and promote the growth of ryegrass. The ryegrass biomass and the copper accumulation in ryegrass were the highest in MAP among all treatments. The effective order of apatite in phytoremediation of copper contaminated field soil was MAP > NAP > OAP, which was attributed to the high adsorption capacity of copper and the strong releasing of phosphate by MAP. PMID:27512641

The compressive strength of the original bone tissue was tested, based on the raw human thigh bone, bovine bone, pig bone and goat bone. The four different bone-like apatites were prepared by calcining the raw bones at 800 degrees C for 8 hours to remove organic components. The comparison of composition and structure of bone-like apatite from different bone sources was carried out with a composition and structure test. The results indicated that the compressive strength of goat bone was similar to that of human thigh bone, reached (135.00 +/- 7.84) MPa; Infrared spectrum (IR), X-ray diffraction (XRD) analysis results showed that the bone-like apatite from goat bone was much closer to the structure and phase composition of bone-like apatite of human bones. Inductively Coupled Plasma (ICP) test results showed that the content of trace elements of bone-like apatite from goat bone was closer to that of apatite of human bone. Energy Dispersive Spectrometer (EDS) results showed that the Ca/P value of bone-like apatite from goat bone was also close to that of human bone, ranged to 1.73 +/- 0.033. Scanning electron microscopy (SEM) patterns indicated that the macrographs of the apatite from human bone and that of goat bone were much similar to each other. Considering all the results above, it could be concluded that the goat bone-like apatite is much similar to that of human bone. It can be used as a potential natural bioceramic material in terms of material properties. PMID:25039141

This work investigates the interaction between the nucleotide adenosine 5‧ monophosphate molecule (AMP) and a biomimetic nanocrystalline carbonated apatite as a model for bone mineral. The analogy of the apatite phase used in this work with biological apatite was first pointed out by complementary techniques. AMP adsorption isotherms were then investigated. Obtained data were fitted to a Sips isotherm with an exponent greater than one suggesting positive cooperativity among adsorbed molecules. The data were compared to a previous study relative to the adsorption of another nucleotide, cytidine monophosphate (CMP) onto a similar substrate, evidencing some effect of the chemical nature of the nucleic base. An enhanced adsorption was observed under acidic (pH 6) conditions as opposed to pH 7.4, which parallels the case of DNA adsorption on biomimetic apatite. An estimated standard Gibbs free energy associated to the adsorption process (ΔG°ads ≅ -22 kJ/mol) intermediate between "physisorption" and "chemisorption" was found. The analysis of the solids after adsorption pointed to the preservation of the main characteristics of the apatite substrate but shifts or enhancements of Raman bands attributed to AMP showed the existence of chemical interactions involving both the phosphate and adenine parts of AMP. This contribution adds to the works conducted in view of better understanding the interaction of DNA/RNA and their constitutive nucleotides and the surface of biomimetic apatites. It could prove helpful in disciplines such as bone diagenesis (DNA/apatite interface in aged bones) or nanomedicine (setup of DNA- or RNA-loaded apatite systems). Also, the adsorption of nucleic acids on minerals like apatites could have played a role in the preservation of such biomolecules in the varying conditions known to exist at the origin of life on Earth, underlining the importance of dedicated adsorption studies.

Apatites from four pairs of samples of Precambrian basement from the western Canadian shield were analyzed by (U-Th)/He thermochronometry to test for the influence of radiation damage on apatite (U-Th)/He dates in this cratonic region. Recent studies have demonstrated that the accumulation of radiation damage increases the apatite He retentivity, so that apatites with a span of effective U concentrations, eU, that experienced the same thermal history may be characterized by a range of closure temperatures. In this investigation, each sample pair consisted of a mafic dike cross-cutting felsic gneisses from a single outcrop or nearby outcrops that contained apatites with a span of eU. The apatites yielded (U-Th)/He dates from 846 to 123 Ma, and were positively correlated with eU within each sample pair. These results can be explained using a model that tracks the evolution of He mobility in response to the accumulation of radiation damage. When coupled with regional geological constraints, the data appear to require partial to complete He loss due to burial and reheating in Phanerozoic time. New apatite fission- track dates and length data were obtained for five of these samples. The apatite fission- track dates are Proterozoic regardless of apatite eU. Thermal history simulations indicate that the apatite fission-track data are compatible with the (U-Th)/He results, although the thermal histories are not identical in detail and the fission-track results alone do not require Phanerozoic heating. Together the data are consistent with burial of this region by ≥ 1 km of Phanerozoic strata that were subsequently denuded, thus pointing toward significant Phanerozoic deposition in the North American cratonic interior hundreds of kilometers east of where previously documented. The results suggest that exploiting radiation damage control on apatite (U-Th)/He dates through investigation of surface sample apatites with a span of closure temperatures can impose tighter

Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In situ relationships between liquid- and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determining particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions, and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP > HAP > CFAP (4.5% CO3) > CFAP (3.4% CO3) > CFAP (2.2% CO3) > FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the coastal sediments analyzed, which supports the hypothesis of apatite formation by an OCP precursor mechanism.

Oxygen isotope ratios (δ18O) of apatite phosphate in fish bones and teeth vary according to the temperature and δ18O of water during formation. Since isotope ratios in apatite are often well preserved over geologic timescales, fish bones and teeth have been used to determine past environmental conditions. Fish scales offer several advantages over bones and teeth: they are relatively common in certain sedimentary basins, and they are more easily identified to species level. Analysis of paired bone and scale samples will be presented. The data indicate that fish scale apatite similarly records environmental conditions during growth. Thus δ18O of apatite phosphate in fish scales may provide useful paleoecological information and also indicate past environmental conditions.

A new method for in situ formation of a calcium apatite permeable reactive barrier that is a groundbreaking technology for containing radioactive/heavy metal contaminants threatening groundwater supplies.

Eight dissolution models of calcium apatites (both fluorapatite and hydroxyapatite) in acids were drawn from the published literature, analyzed and discussed. Major limitations and drawbacks of the models were conversed in details. The models were shown to deal with different aspects of apatite dissolution phenomenon and none of them was able to describe the dissolution process in general. Therefore, an attempt to combine the findings obtained by different researchers was performed which resulted in creation of the general description of apatite dissolution in acids. For this purpose, eight dissolution models were assumed to complement each other and provide the correct description of the specific aspects of apatite dissolution. The general description considers all possible dissolution stages involved and points out to some missing and unclear phenomena to be experimentally studied and verified in future. This creates a new methodological approach to investigate reaction mechanisms based on sets of affine data, obtained by various research groups under dissimilar experimental conditions. PMID:25237611

Highlights: {yields} Cytoplasmic stability of plasmid DNA is enhanced by fluoride incorporation into carbonate apatite carrier. {yields} Fluoridated carbonate apatite promotes a robust increase in transgene expression. {yields} Controlled dissolution of fluoridated carbonate apatite in endosomal acidic environment might buffer the endosomes and prevent degradation of the released DNA. -- Abstract: Intracellular delivery of a functional gene or a nucleic acid sequence to specifically knockdown a harmful gene is a potential approach to precisely treat a critical human disease. The intensive efforts in the last few decades led to the development of a number of viral and non-viral synthetic vectors. However, an ideal delivery tool in terms of the safety and efficacy has yet to be established. Recently, we have developed pH-sensing inorganic nanocrystals of carbonate apatite for efficient and cell-targeted delivery of gene and gene-silencing RNA. Here we show that addition of very low level of fluoride to the particle-forming medium facilitates a robust increase in transgene expression following post-incubation of the particles with HeLa cells. Confocal microscopic observation and Southern blotting prove the cytoplasmic existence of plasmid DNA delivered by likely formed fluoridated carbonate apatite particles while degradation of plasmid DNA presumably by cytoplasmic nucleases was noticed following delivery with apatite particles alone. The beneficial role of fluoride in enhancing carbonate apatite-mediated gene expression might be due to the buffering potential of generated fluoridated apatite in endosomal acidic environment, thereby increasing the half-life of delivered plasmid DNA.

A novel bioactive porous apatite-wollastonite/chitosan composite coating was prepared by electrophoretic deposition. The influence of synthesis parameters like pH of suspension and current density was studied and optimized. X-ray diffraction confirmed crystalline phase of apatite-wollastonite in powder as well as composite coating with coat crystallinity of 65%. Scanning electron microscope showed that the porosity had interconnections with good homogeneity between the phases. The addition of chitosan increased the adhesive strength of the composite coating. Young's modulus of the coating was found to be 9.23 GPa. One of our key findings was sheet-like apatite growth unlike ball-like growth found in bioceramics. Role of chitosan was studied in apatite growth mechanism in simulated body fluid. In presence of chitosan, dense negatively charged surface with homogenous nucleation was the primary factor for sheet-like evolution of apatite layer. The results suggest that incorporation of chitosan with apatite-wollastonite in composite coating could provide excellent in vitro bioactivity with enhanced mechanical properties. PMID:19253015

More than 1000 analyses have been tabulated of the distribution of the lanthanides and yttrium in minerals of the apatite group, recalculated to atomic percentages. Average compositions have been calculated for apatites from 14 types of rocks. These show a progressive change of composition from apatites of granitic pegmatites, highest in the heavy lanthanides and yttrium, to those from alkalic pegmatites, highest in the light lanthanides and lowest in yttrium. This progression is clearly shown in plots of S (= at % La+Ce+Pr) vs the ratio La/Nd and of S vs the ratio 100Y/(Y+Ln), where Ln is the sum of the lanthanides. Apatites of sedimentary phosphorites occupy a special position, being relatively depleted in Ce and relatively enriched in yttrium and the heavy lanthanides, consequences of deposition from sea water. Apatites associated with iron ores are close in composition to apatites of carbonatites, alkalic ultramafic, and ultramafic rocks, being enriched in the light lanthanides and depleted in the heavy lanthanides. Their compositions do not support the hypothesis of Parak that the Kiruna-type ores are of sedimentary origin. Table 9 and Figures 1-3 show the dependence of lanthanide distribution on the nature of the host rock. Although a given analysis of the lanthanides does not unequivocally permit certain identification of the host rock, it can indicate a choice of highly probable host rocks.

Apatite is a common accessory mineral in igneous, metamorphic and clastic sedimentary rocks. It is a nearly ubiquitous accessory phase in igneous rocks, is common in metamorphic rocks of pelitic, carbonate, basaltic, and ultramafic composition and is virtually ubiquitous in clastic sedimentary rocks. In contrast to the polycyclic behavior of the stable heavy mineral zircon, apatite is unstable in acidic groundwaters and has limited mechanical stability in sedimentary transport systems. Apatite has many potential applications in provenance studies, particularly as it likely represents first-cycle detritus. Fission track and U-Pb dating are very powerful techniques in apatite provenance studies. They yield complementary information, with the apatite fission-track system yielding low-temperature exhumation ages and the U-Pb system yielding high-temperature cooling ages which constrain the timing of apatite crystallization. This study focuses on integrating apatite fission track and U-Pb dating by the LA-ICPMS method. Our approach is intentionally broad in scope, and is applicable to any quadrupole or rapid-scanning magnetic-sector LA-ICPMS system. Calculating uranium concentrations in fission-track dating by LA-ICPMS increases the speed of analysis and sample throughput compared to the conventional external detector method and avoids the need for neutron irradiation (Hasebe et al., 2004). LA-ICPMS-based uranium measurements in apatite are measured relative to an internal concentration standard (typically 43Ca). Ca in apatite is not always stochiometric as minor cations (Mn2+, Sr2+, Ba2+ and Fe2+) and REE can substitute with Ca2+. These substitutions must be quantified by multi-elemental LA-ICPMS analyses. Such data are also useful for discriminating between different apatite populations in sedimentary or volcaniclastic rocks based on their trace-element chemistry. Low U, Th and radiogenic Pb concentrations, elevated common Pb / radiogenic Pb ratios and U-Pb elemental

Apatite (U-Th)/He thermochronology is commonly used to study landscape evolution and potential links between climate, erosion and tectonics. The technique relies on a quantitative understanding of (i) helium diffusion kinetics in apatite, (ii) an evolving 4He concentration, (iii) accumulating damage to the crystal lattice caused by radioactive decay[1], and (iv) the thermal annealing of such damage[2],[3], which are each functions of both time and temperature. Uncertainty in existing models of helium diffusion kinetics has resulted in conflicting conclusions, especially in settings involving burial heating through geologic time. The effects of alpha recoil damage annealing are currently assumed to follow the kinetics of fission track annealing (e.g., reference [3]), although this assumption is difficult to fully validate. Here, we present results of modeling exercises and a suite of experiments designed to interrogate the effects of damage annealing on He diffusivity in apatite that are independent of empirical calibrations of fission track annealing. We use the existing experimental results for Durango apatite[2] to develop and calibrate a new function that predicts the effects of annealing temperature and duration on measured diffusivity. We also present a suite of experiments conducted on apatite from Sierra Nevada, CA granite to establish whether apatites with different chemical compositions have the same behavior as Durango apatite. Crystals were heated under vacuum to temperatures between 250 and 500°C for 1, 10, or 100 hours. The samples were then irradiated with ~220 MeV protons to produce spallogenic 3He, the diffusant then used in step-heating diffusion experiments. We compare the results of these experiments and model calibrations to existing models. Citations: [1]Shuster, D., Flowers R., and Farley K., (2006), EPSL 249(3-4), 148-161; [2]Shuster, D. and Farley, K., (2009), GCA 73 (1), 6183-6196; [3]Flowers, R., Ketcham, R., Shuster, D. and Farley, K

Study focused on the interaction of adsorbate with poorly crystalline apatitic calcium phosphates analogous to bone mineral. Calcium phosphates prepared in water-ethanol medium at physiological temperature (37 °C) and neutral pH, their Ca/P ratio was between 1.33 and 1.67. Adsorbate used in this paper takes the mixture form of two essential amino acids L-lysine and DL-leucine which have respectively a character hydrophilic and hydrophobic. Adsorption and release are investigated experimentally; they are dependent on the phosphate type and on the nature of adsorbate L-lysine, DL-leucine and their mixture. Adsorption of mixture of amino acids on the apatitic calcium phosphates is influenced by the competition between the two amino acids: L-lysine and DL-leucine which exist in the medium reaction. The adsorption kinetics is very fast while the release kinetics is slow. The chemical composition of apatite has an influence on both adsorption and release. The interactions adsorbate-adsorbent are electrostatic type. Adsorption and release reactions of the amino acid mixture are explained by the existence of the hydrated surface layer of calcium phosphate apatite. The charged sbnd COOsbnd and sbnd NH3+ of adsorbates are the strongest groups that interact with the surface of apatites, the adsorption is mainly due to the electrostatic interaction between the groups sbnd COOsbnd of amino acids and calcium Ca2+ ions of the apatite. Comparative study of interactions between adsorbates (L-lysine, DL-leucine and their mixture) and apatitic calcium phosphates is carried out in vitro by using UV-vis and infrared spectroscopy IR techniques.

Khanlogh iron deposit lies on Sabzehvar-Ghoochan Cenozoic magmatic belt in northwest of Neyshaboor, NE Iran. The lithologic units in this area include a series of sub-volcanic intrusive rocks like diorite porphyry, quartz-diorite porphyry, and micro-granodiorite of Oligocene age. Mineralization in this area occurred as veins, dissemination, and open space filling in brecciated zones within the host sub-volcanic intrusive bodies. Three distinct types of mineral associations can be distinguished, (1) diopside-magnetite, (2) magnetite-apatite, and (3) apatite-calcite. Microscopic examinations along with SEM and EPMA studies demonstrated that magnetite is the most common ore mineral occurring as solitary crystals. The euhedral magnetite crystals are accompanied by lamellar destabilized ilmenite and granular fluorapatite in magnetite-apatite ores. The results of EPMA revealed that the lamellar ilmenite, relative to host magnetite crystal, is notably enriched in MgO and MnO (average of 3.3 and 2.6 wt%, respectively; n=5), whereas magnetite is slighter enriched in Ti (TiO2 around 1.8 wt%) being average of MgO, MnO and V2O3 of 0.6wt%, 0.2wt%, and 0.6 wt% (respectively; n=20). Minerals such as chlorapatite, calcite, and chalcedony are also present in the magnetite-apatite ores. The samples from apatite-calcite ores contain coarse crystals of apatite and rhomboedral calcite. The plot of the EPMA data of Khanlogh iron ore samples on diagram of TiO2-V2O5 (Hou et al, 2011) illustrated that the data points lies between the well-known Kiruna and El Laco (Chile) iron deposits. The magnetite crystals in the sub-volcanic host rocks were possibly formed by immiscible iron oxide fluids during magmatic stage. However, the magnetite and apatite existing in the veins and breccia zones may have developed by high temperature hydrothermal fluids. Studies done by Purtov and Kotelnikova (1993) proved that the proportion of Ti in magnetite is related to fluoride complex in the hydrothermal

The mineralized troctolitic Bathtub intrusion (Duluth Complex, NE-Minnesota) is known for its famous Cu-Ni-Sulfide±PGM Babbitt deposit, where platinum group minerals (PGMs) are either hosted by primary magmatic sulfides (base metal sulfides) or associated with hydrothermally altered portions. This secondary generation of PGMs is present in alteration patches and suggests the involvement of hydrothermal fluids in the mobilization of platinum-group elements (PGEs). Accessory fluorapatite in these samples reveals besides H2O- and CO2-rich primary fluid inclusions, textural and compositional variations that also record magmatic and metasomatic events. Based on detailed back-scattered electron imaging (BSE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS), a primary magmatic origin is reflected by homogeneous or zoned grains, where zoning patterns are either concentric or oscillatory, with respect to LREE. Late magmatic to hydrothermal processes are indicated by grains with bright LREE-enriched rims or conversion textures with REE-enriched patches in the interior of the apatite. A metasomatic formation of monazite from apatite is documented by the presence of monazite inclusions in apatite and newly grown monazite at altered apatite rims. They formed by the release of REEs from the apatite during a fluid-induced alteration, based on the coupled substitution Ca2+ + P5+ = REE3+ + Si4+ (Rønsbo 1989; Rønsbo 2008). Samples with monazite inclusions in apatite further display occurrences of PGMs associated with hydrothermal alteration patches (chlorite + amphibole). The presence of H2O- and CO2-rich fluid inclusions in apatite, the metasomatically induced monazite growth, as well as the occurrence of PGMs in hydrothermally alteration zones, also suggest the involvement of aqueous chloride complexes in a H2O dominated fluid in the transportation of LREE and redistribution of the second generation of PGEs. Rønsbo, J.G. (1989): Coupled substitutions

Induction of an apatite-forming ability on a nano-composite of a ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP) and alumina (Al2O3) polycrystals via chemical treatment with aqueous solutions of H3PO4, H2SO4, HCl, or NaOH has been investigated. The Ce-TZP/Al2O3 composite is attractive as a load-bearing bone substitute because of its mechanical properties. The chemical treatments produced Zr-OH surface functional groups, which are known to be effective for apatite nucleation in a body environment. The composite, after chemical treatment, was shown to form a bonelike apatite layer when immersed in a simulated body fluid containing ion concentrations nearly equal to those in human blood plasma. This implies that it may form apatite in the living body and bond to living bone through the apatite layer. This type of bioactive Ce-TZP/Al2O3 composite is therefore expected to be useful as a bone substitute, even under load-bearing conditions. PMID:11857434

Previous studies have shown that bredigite (Ca7MgSi4O16) bioceramics possessed excellent biocompatibility, apatite-mineralization ability and mechanical properties. In this paper, the bredigite coating on Ti-6Al-4 V substrate was prepared by plasma spraying technique. The main compositions of the coating were bredigite crystal phase with small parts of amorphous phases. The bonding strength of the coating to Ti-6Al-4 V substrate reached 49.8 MPa, which was significantly higher than that of hydroxyapatite coating and other silicate-based bioceramic coatings prepared by same method. After immersed in simulated body fluid for 2 days, a distinct apatite layer was deposited on the surface of bredigite coating, indicating that the prepared bredigite coating has excellent apatite-mineralization ability. The prepared bredigite coating supported the attachment and proliferation of rabbit bone marrow stem cells. The proliferation level of bone marrow stem cells was significantly higher than that on the hydroxyapatite coating. Our further study showed that the released SiO4 (4-) and Mg(2+) ions from bredigite coating as well as the formed nano-apatite layer on the coating surface might mainly contribute to the improvement of cell proliferation. The results indicated that the bredigite coating may be applied on orthopedic implants due to its excellent bonding strength, apatite mineralization and cytocompatibility. PMID:24131918

Sequestration of uranium as insoluble phosphate phases appears to be a promising alternative for treating the uranium-contaminated groundwater at the Hanford 300 Area. The proposed approach involves both the direct formation of autunite by the application of a polyphosphate mixture, as well as the formation of apatite in the aquifer as a continuing source of phosphate for long-term treatment of uranium. After a series of bench-scale tests, a field treatability test was conducted in a well at the 300 Area. The objective of the treatability test was to evaluate the efficacy of using polyphosphate injections to treat uranium-contaminated groundwater in situ. A test site consisting of an injection well and 15 monitoring wells was installed in the 300 Area near the process trenches that had previously received uranium-bearing effluents. The results indicated that while the direct formation of autunite appears to have been successful, the outcome of the apatite formation of the test was more limited. Two separate overarching issues impact the efficacy of apatite remediation for uranium sequestration within the 300 Area: 1) the efficacy of apatite for sequestering uranium under the present geochemical and hydrodynamic conditions, and 2) the formation and emplacement of apatite via polyphosphate technology. This paper summarizes these issues.

Oleate adsorption at an apatite surface was investigated by ex-situ Fourier transform infrared internal reflection spectroscopy (FTIR/IRS). Adsorption isotherms have been determined using an apatite internal reflection element (IRE) and it has been found that pH has a significant influence on oleate adsorption by apatite. At pH 8.0 and 20 C, oleate adsorption density increases monotonically as equilibrium oleate concentration increases from 5 {times} 10{sup {minus}6} to 1 {times} 10{sup {minus}3} M. These results are in contrast to the results at pH 9.5 and 20 C in which case the adsorption density is limited to that corresponding to approximately monolayer coverage. Oleate adsorption by apatite was compared to oleate adsorption by fluorite and calcite and the different adsorption behavior at these three mineral surfaces is attributed to the differences in the densities of surface calcium sites and to the differences in the solubilities of these minerals. Contact angles have been measured at the apatite IRE surface and it has been demonstrated that both the amount and the nature of the adsorbed species influence the hydrophobic state of the surface.

Biomimetic nanocrystalline calcium-deficient apatite compounds are particularly attractive for the setup of bioactive bone-repair scaffolds due to their high similarity to bone mineral in terms of chemical composition, structural and substructural features. As such, along with the increasingly appealing development of moderate temperature engineered routes for sample processing, they have widened the armamentarium of orthopedic and maxillofacial surgeons in the field of bone tissue engineering. This was made possible by exploiting the exceptional surface reactivity of biomimetic apatite nanocrystals, capable of easily exchanging ions or adsorbing (bio)molecules, thus leading to highly-versatile drug delivery systems. In this contribution we focus on the preparation of hybrid materials combining biomimetic nanocrystalline apatites and enzymes (lysozyme and subtilisin). This paper reports physico-chemical data as well as cytotoxicity evaluations towards Cal-72 osteoblast-like cells and finally antimicrobial assessments towards selected strains of interest in bone surgery. Biomimetic apatite/enzyme hybrids could be prepared in varying buffers. They were found to be non-cytotoxic toward osteoblastic cells and the enzymes retained their biological activity (e.g. bond cleavage or antibacterial properties) despite the immobilization and drying processes. Release properties were also examined. Beyond these illustrative examples, the concept of biomimetic apatites functionalized with enzymes is thus shown to be useable in practice, e.g. for antimicrobial purposes, thus widening possible therapeutic perspectives. PMID:24258399

Plasma electrolytic oxidation (PEO) was employed to grow different porous titania structures on Ti6Al4V alloy (TC4) substrate using various parameters. It was found that the PEO voltage and working frequency could affect the morphology, the pore size, the pore density, the thickness and the phase composition of titania structures. Thereafter, three typical porous titania structures with nanosize pores, microsize pores and microsize grooves were respectively selected to estimate their bioactivity using SBF immersion test. After soaking at different durations (3-28d), the surface morphology, the chemical composition as well as the phase structure of deposited apatite layers on porous titania were evaluated using SEM, EDS, and XRD. The formation of various biomimetic apatite layers indicated the different influence due to the characteristics of porous titania structures. The porous titania structure with nanosize pores could induce a fast apatite growth at the early immersion stage (~7d), while the one with microsize pores exhibited the best apatite inducing ability at long term immersion (~28d). Based on the experimental results, the formation mechanism of biomimetic apatite affected by the pore structure of titania was discussed as well. PMID:27207066

The apatite (U-Th)/He (AHe) system has rapidly become a very popular thermochronometer to constrain burial and exhumation phases in a variety of geological contexts. However, the interpretation of AHe data depends on a precise knowledge of He diffusion in apatite. Several studies suggest that radiation damage generated by U and Th decay can create traps for He atoms, increasing He retention for irradiated minerals. The radiation damage also anneals with temperature and the amount of damage in an apatite crystal is at any time a balance between production and annealing, controlled by U-Th concentration, grain chemistry and thermal history (Flowers et al., 2009; Gautheron et al., 2009; 2013). However the models are not well constrained and do not fully explain the mechanism of He retention. In order to have a deeper insight on this issue, multidisciplinary studies on apatite combining diffusion experiments by Elastic Recoil Diffusion Analysis (ERDA) with a multi-scale theoretical diffusion calculation based on Density Functional Theory (DFT) and Kinetic Monte Carlo were performed. ERDA experiments were conducted on different macro-crystals, and we probed the shape of a He profile implanted into a planar and polished surface of the crystal. The helium profile evolves with temperature and allows quantifying the He diffusivity and damage impact. Additionally, DFT calculations of a damage-free crystal of apatite with different F and Cl compositions, in similar proportion as natural ones, have been run to find the favored paths of a helium atom between interstitial sites, leading to a computation of the activation energy and the diffusion coefficient. We show that damage free apatite crystals are characterized by low retention behavior and closure temperature range from 33-36°C for pure F-apatite to higher value for Cl riche apatite (up to 12°C higher), for typical grain size and cooling rate (Mbongo-Djimbi et al., in review). Using ERDA and DFT approaches, we

Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

Diffusion experiments were carried out on natural apatite crystals that were immersed in molten light rare earth element (REE) chloride salt at temperatures between 900 and 1150 °C for periods up to 35 days. Electron microprobe analysis of the crystals showed that light REEs replaced Ca according to electronic balance, i.e. 2 REE3+ for 3 Ca2+. These diffusion profiles indicate that a maximum amount of substitution in the structure occurs when two of the ten Ca ions in apatite are replaced by the REE diffusing elements. Anisotropic diffusion is observed between a and c crystallographic directions. Comparison of maximum distance indicates that the larger ions move more easily in the apatite structure. We conclude that the light REEs diffuse within the channel structures of the mineral, and that this diffusion is controlled by the substitution type of elements in the calcium sites. To cite this article: A. Iqdari et al., C. R. Geoscience 335 (2003).

An iron oxide containing calcium phosphate-silicate hydroxyapatite was synthesized by calcination at 900 °C of a sample obtained by precipitation in basic aqueous solution of Ca, P, Si, Fe and Mg containing acidic solution made from dissolution of natural minerals. XRD and FTIR were used for crystallographic characterization of the main apatitic phase. Its composition was determined using ICP-AES. EDX coupled with SEM and TEM evidenced the heterogeneity of this compound and the existence of iron-magnesium oxide. Magnetic analyses highlighted that this phase was non-stoichiometric magnesioferrite (Mg 1.2Fe 1.8O 3.9) spherical nanoparticles. Those analyses also put into evidence the role of calcination in synthesis. Carbonates detected by FTIR and estimated by SEM-EDX in non-calcinated sample were removed from apatitic structure, and crystallization of apatite was enhanced during heating. Moreover, there was phase segregation that led to magnesioferrite formation.

Oxygen isotopes of biogenic apatite have been widely used to reassess anomalous temperatures inferred from oxygen isotope ratios of ancient biogenic calcite, more prone to diagenetic alteration. However, recent studies have highlighted that oxygen isotope ratios of biogenic apatite differ dependent on used analytical techniques. This questions the applicability of the phosphate-water fractionation equations established over 25 years ago using earlier analytical techniques to more recently acquired data. In this work we present a new phosphate-water oxygen isotope fractionation equation based on oxygen isotopes determined on fish raised in aquariums at controlled temperature and with monitored water oxygen isotope composition. The new equation reveals a similar slope, but an offset of about + 2‰ to the earlier published equations. This work has major implications for paleoclimatic reconstructions using oxygen isotopes of biogenic apatite since calculated temperatures have been underestimated by about 4 to 8 °C depending on applied techniques and standardization of the analyses.

In 2004, the U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory (PNNL), and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at the 100-N Area would include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary. Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing strontium-90 flux to the Columbia River. This Quality Assurance Project Plan provides the quality assurance requirements and processes that will be followed by staff working on the PNNL Apatite Investigation at 100-NR-2 Project. The plan is designed to be used exclusively by project staff.

Wrangel Island is part of a regional structural high that forms the continuation of the offshore Herald Arch and Chukchi Platform of Alaska. It is flanked on the north by the deep North Chukchi Basin, which in addition to Paleozoic strata, is inferred to contain up to 12 km of Beaufortian and Brookian (Late Jurassic to Tertiary) sediments (Dinkelman et al., 2008). To the south, ~E-W trending faults bound the Longa Basin that separates Wrangel from mainland Chukotka. This basin lies along strike of the early Tertiary Hope Basin in the Alaskan offshore. Wrangel Island itself exposes a broad, doubly-plunging anticlinorium-like structure cored by Neoproterozoic basement and flanked by Paleozoic shelf successions and a thick section of Triassic turbidites, representing about 5-7 km of structural section. The structural geology of Wrangel Island has been interpreted to represent a north-vergent Mesozoic fold and thrust belt linked by seismic reflection to the Herald Arch and then to the Lisburne Hills and the Brooks Range foreland fold and thrust belt (e.g. Kos’ko et al., 1993). However, deformation differs considerably from typical foreland fold-thrust structures of the Brooks Range as it is penetrative, involves large strains, and occurred under greenschist facies metamorphic conditions. Parts of the sequence exhibit mylonitic fabrics. Apatite fission track thermochronology of rocks from Wrangel Island can establishes the age of cooling to temperatures below ~ 100° C, providing temporal constraints on the uplift and erosional history of rocks that form this regional structural high. We analyzed seven fission track samples from a 9-km long N-S transect along the Kishchnikov River, from Triassic strata on the southern flank of the anticlinal structure to Devonian(?)-Mississippian feldspathic grits, conglomerates, and underlying Neoproterozoic igneous basement rocks in its core. All samples yielded statistically indistinguishable fission track ages averaging about 95

Hydride (H(-)) ions and electrons in channel sites of the lattice of calcium phosphate apatites are characterized. Solid-state chemical reduction using TiH2 is effective for doping of H(-) ions into apatites. Irradiation of the H(-) ion-doped apatite with ultraviolet (UV) light induces green coloration. Electron paramagnetic resonance (EPR) reveals that this colour centre is attributed to electrons captured at a vacant anion site in the crystallographic channel, forming F(+) centres. Transient H(0) atoms are detected at low temperatures by EPR. The concentration of UV-induced electrons in the apatite at room temperature decays according to second-order kinetics because of the chemical reactions involving two electrons; overall, electron generation and thermal decay can be described as: H(-) + O(2-) ↔ 2e(-) + OH(-). (1)H magic angle spinning nuclear magnetic resonance spectroscopy is used to identify H(-) ions in the apatite, which are characterized by a chemical shift of +3.4 ppm. Various types of O-H groups including OH(-) ions in the channel and protons bound to phosphate groups are concurrently formed, and are identified by considering the relationship between the O-H stretching frequency and the (1)H chemical shift. The complementary results obtained by EPR and NMR reveal that the H(-) ions and transient H(0) atoms are located at the centre of Ca3 triangles in the apatite, while the electrons are located in the centre of Ca6 octahedra. These findings provide an effective approach for identifying new classes of mixed-oxide-hydride or -electride crystals. PMID:26928237

ATP is a well-known energy supplier in cells. The idea to associate ATP to pharmaceutical formulations/biotechnological devices to promote cells activity by potentially modulating their microenvironment thus appears as an appealing novel approach. Since biomimetic nanocrystalline apatites have shown great promise for biomedical applications (bone regeneration, cells diagnostics/therapeutics, …), thanks to a high surface reactivity and an intrinsically high biocompatibility, the present contribution was aimed at exploring ATP/apatite interactions. ATP adsorption on a synthetic carbonated nanocrystalline apatite preliminarily characterized (by XRD, FTIR, Raman, TG-DTA and SEM-EDX) was investigated in detail, pointing out a good agreement with Sips isothermal features. Adsorption characteristics were compared to those previously obtained on monophosphate nucleotides (AMP, CMP), unveiling some specificities. ATP was found to adsorb effectively onto biomimetic apatite: despite smaller values of the affinity constant KS and the exponential factor m, larger adsorbed amounts were reached for ATP as compared to AMP for any given concentration in solution. m < 1 suggests that the ATP/apatite adsorption process is mostly guided by direct surface bonding rather than through stabilizing intermolecular interactions. Although standard ΔGads ° was estimated to only -4 kJ/mol, the large value of Nmax led to significantly negative effective ΔGads values down to -33 kJ/mol, reflecting the spontaneous character of adsorption process. Vibrational spectroscopy data (FTIR and Raman) pointed out spectral modifications upon adsorption, confirming chemical-like interactions where both the triphosphate group of ATP and its nucleic base were involved. The present study is intended to serve as a basis for future research works involving ATP and apatite nanocrystals/nanoparticles in view of biomedical applications (e.g. bone tissue engineering, intracellular drug delivery, …).

The chemical interaction between DNA macromolecules and hard tissues in vertebrate is of foremost importance in paleogenetics, as bones and teeth represent a major substrate for the genetic material after cell death. Recently, the empirical hypothesis of DNA "protection" over time thanks to its adsorption on hard tissues was revisited from a physico-chemical viewpoint. In particular, the existence of a strong interaction between phosphate groups of DNA backbone and the surface of apatite nanocrystals (mimicking bone/dentin mineral) was evidenced on an experimental basis. In the field of nanomedicine, DNA or RNA can be used for gene transport into cells, and apatite nanocarriers then appear promising. In order to shed some more light on interactions between DNA molecules and apatite, the present study focuses on the adsorption of a "model" nucleotide, cytidine 5' monophosphate (CMP), on a carbonated biomimetic apatite sample. The follow-up of CMP kinetics of adsorption pointed out the rapidity of interaction with stabilization reached within few minutes. The adsorption isotherm could be realistically fitted to the Sips model (Langmuir-Freundlich) suggesting the influence of surface heterogeneities and adsorption cooperativity in the adsorption process. The desorption study pointed out the reversible character of CMP adsorption on biomimetic apatite. This contribution is intended to prove helpful in view of better apprehending the molecular interaction of DNA fragments and apatite compounds, independently of the application domain, such as bone diagenesis or nanomedicine. This study may also appear informative for researchers interested in the origins of life on Earth and the occurrence and behavior of primitive biomolecules. PMID:26117294

Addition of an amendment or reagent to soil/sediment is a technique that can decrease mobility and reduce bioavailability of uranium (U) and other heavy metals in the contaminated site. According to data from literature and results obtained in field studies, the general mineral class of apatites was selected as a most promising amendment for in situ immobilization/remediation of U. In this work we presented theoretical assessment of stability of U(VI) in four apatite systems (hydroxyapatite (HAP), North Carolina Apatite (NCA), Lisina Apatite (LA), and Apatite II) in order to determine an optimal apatite soil amendment which could be used for in situ remediation of uranium. In this analysis we used a theoretical criterion which is based on calculation of the ion-ion interaction potential, representing the main term of the cohesive energy of the matrix/pollutant system. The presented results of this analysis indicate (i) that the mechanism of immobilization of U by natural apatites depends on their chemical composition and (ii) that all analyzed apatites represent, from the point of view of stability, promising materials which could be used in field remediation of U-contaminated sites. PMID:15885755

The mineral apatite can incorporate all of the major magmatic volatile species into its structure. Where melt inclusions are not available, magmatic apatite may therefore represent an opportunity to quantify volatile concentrations in the pre-eruptive melt. We analysed apatites and matrix glasses from andesites and dacites erupted from Santiaguito Volcano, Guatemala, between the 1920s and 2002. X-ray mapping shows complex zoning of sulphur in the apatite grains, but typically with sulphur-rich cores and sulphur-poor rims. Apatite microphenocrysts are enriched in F and depleted in Cl relative to inclusions. Matrix glasses are dacite to rhyolite and contain low F but up to 2400 ppm Cl. Overall, the data are consistent with progressive depletion of Cl in the most evolved melts due to crystallisation and degassing. In the absence of pristine melt inclusions, we used apatite, together with published partitioning data, to reconstruct the likely volatile contents of the pre-eruptive melt, and hence estimate long-term average gas emissions of SO2, HF and HCl for the ongoing eruption. The data indicate time-averaged SO2 emissions of up to 157 tonnes/day, HCl of 74-1382 tonnes/day and up to 196 tonnes/day HF. Apatite may provide a useful measure of long-term volatile emissions at volcanoes where direct emissions measurements are unavailable, or for comparison with intermittent gas sampling methods. However, significant uncertainty remains regarding volatile distribution coefficients for apatite, and their variations with temperature and pressure.

γ-Methacryloxypropyltrimethoxysilane (γ-MPS) was grafted to high-density polyethylene, polyamide and silicone rubber substrates by the emulsion polymerization procedure in order to provide these organic polymers with in vitro apatite-forming ability. The contact angles towards distilled water of the γ-MPS-grafted specimens were lower than those of the original organic polymer specimens, indicating that the grafted substrates were more hydrophilic. The in vitro apatite formation in a simulated body fluid (Kokubo solution) was confirmed for several of the γ-MPS-grafted specimens. PMID:16849191

Bioactive membranes for guided tissue regeneration would be of value for periodontal therapy. Chitosan-multiwall carbon nanotube (CS-MWNT) composites were treated to deposit nanoscopic apatite for MWNT proportions of 0-4 mass%. Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and X-ray diffraction were used for characterization. Apatite was formed on the CS-MWNT composites at low MWNT concentrations, but the dispersion of the MWNT affects the crystallite size and the Ca/P molar ratio of the composite. The smallest crystallite size was 9 nm at 1 mass% MWNT.

This Quality Assurance Project Plan provides the quality assurance requirements and processes that will be followed by staff working on the 100-NR-2 Apatite Project. The U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N would include apatite sequestration as the primary treatment, followed by a secondary treatment. The scope of this project covers the technical support needed before, during, and after treatment of the targeted subsurface environment using a new high-concentration formulation.

The apatite crystal structure is capable of incorporating H2O, F and Cl, as well as trace CO2 and sulphur. These can be related to parental magma compositions through application of a series of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994), permitting apatite crystals to preserve a record of all major volatile species in the melt. Furthermore, due to the general incompatibility of P in other rock-forming minerals, apatite is ubiquitous in igneous systems and often begins crystallising early, such that apatite inclusions within phenocrysts record melt volatile contents throughout magmatic differentiation. In this work, we compare the compositions of apatite inclusions and microphenocrysts with pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy. These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to determine a time-series of magmatic volatile evolution in the build-up to eruption. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset during ascent, due to rapid H diffusion through the phenocryst hosts (Woods et al., 2000). Given the rapid diffusivity of volatiles in apatite (Brenan, 1993), preservation of undersaturated compositions in microphenocrysts suggests that saturation was only achieved a few days to months before eruption and that it may have been the transition into a volatile-saturated state that ultimately triggered eruption. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Gualda et al., 2012

The biomimetic deposition rate of apatite for Ti-6Al-4V was found to be greater than that for Ti-6Al-7Nb in regular 1 × Modified SBF. The coating of collagen was found to enhance the biomimetic deposition of apatite on Ti-6Al-4V and Ti-6Al-7Nb. The nucleation and growth of the apatite deposition layer was faster on collagen coated Ti alloys. An interesting observation is that the granular structure became less clear and the nodular boundary became obscure in apatite deposited on the collagen-coated Ti alloys. The ill-defined granular structure may be associated with the presence of more amorphous calcium phosphate. The morphology of apatite nodules was found to be modified by collagen coating and collagen addition.

The quantification of the different parameters influencing He diffusion in apatite is an important issue for the interpretation of (U-Th)/He thermochronometric ages. Key issues include understanding the role of chemical composition and the mechanism modifying diffusivity by radiation damage, both requiring a realistic description at the atomic level. In this contribution, we restrict ourselves on the influence of the chemical composition especially on the effect of Cl-atoms on the He diffusion in the damage-free apatite crystal. For this purpose, a multi-scale theoretical diffusion study has been conducted using periodic Density Functional Theory calculations for two different apatite compositions (pure fluorine apatite and apatite with one chlorine and 3 fluorine atoms per cell called Cl0.25-apatite) representative of damage-free crystals. Different He insertion sites and diffusion pathways are first investigated. The Density Functional Theory approach coupled to the Nudged Elastic Band method is used to determine the energy barriers between the insertion sites. A statistical method, based on Transition State Theory, is used to compute the jump rate between sites and the different results are used as output for a 3D random walk simulation, which determines the diffusion trajectories and the diffusion coefficients. The calculated diffusion coefficients for pure F-apatite exhibit a slightly anisotropic behavior with an activation energy Ea = 95.5 kJ/mol and a frequency factor D0 = 1.9 × 10-3 cm2/s along the c axis; Ea = 106.1 kJ/mol and D0 = 4.1 × 10-3 cm2/s in the plane orthogonal to c. Closure temperatures for a 60 μm grain radius and 10 °C/Ma cooling rate range from 33 to 36 °C and depend on crystal geometry for a given grain size. Surprisingly, even though He diffusion is strongly blocked across the Cl atoms in Cl0.25-apatite, where Ea is significantly higher (166.7 kJ/mol), He atoms can still diffuse along the c axis through workaround pathways. Closure

Fishbone, a natural, apatite rich substance, was examined for suitability as a substitute for hydroxyapatite in the sequestering of aqueous divalent heavy metal ions. The fishbone exhibited lower metal removal capacity than pure hydroxyapatite, due primarily to its purity ( approximately 70% apatite equivalent). In other ways the fishbone behaves in a similar manner as pure hydroxyapatite in the sequestration process. It was observed that it can remove all Pb(2+), Cu(2+), Cd(2+) and Ni(2+) to below detectable levels as measured by inductively coupled plasma atomic absorption, and the rate of reaction with either Zn(2+), Ni(2+), or Pb(2+) was also found to be similar to hydroxyapatite. Also, a two level, three variable full factorial design was performed for the Pb/apatite reaction and both apatites performed similarly. The main difference, besides capacity, was on exposure to high (2.4 mM) Pb concentrations. The fishbone removed less of the Pb(2+) than capacity correction predicted. PMID:10536284

Bone is a composite material, in which collagen fibrils form a scaffold for a highly organized arrangement of uniaxially oriented apatite crystals1,2. In the periodic 67 nm cross-striated pattern of the collagen fibril3–5, the less dense 40-nm-long gap zone has been implicated as the place where apatite crystals nucleate from an amorphous phase, and subsequently grow6–9. This process is believed to be directed by highly acidic non-collagenous proteins6,7,9–11; however, the role of the collagen matrix12–14 during bone apatite mineralization remains unknown. Here, combining nanometre-scale resolution cryogenic transmission electron microscopy and cryogenic electron tomography15 with molecular modelling, we show that collagen functions in synergy with inhibitors of hydroxyapatite nucleation to actively control mineralization. The positive net charge close to the C-terminal end of the collagen molecules promotes the infiltration of the fibrils with amorphous calcium phosphate (ACP). Furthermore, the clusters of charged amino acids, both in gap and overlap regions, form nucleation sites controlling the conversion of ACP into a parallel array of oriented apatite crystals. We developed a model describing the mechanisms through which the structure, supramolecular assembly and charge distribution of collagen can control mineralization in the presence of inhibitors of hydroxyapatite nucleation. PMID:20972429

The main purposes of fission track thermochronology are unravelling the thermal histories of sedimentary basins, determining uplift and denudation rates, identifying the structural evolution of orogenic belts, determining sedimentary provenance, and dating volcanic rocks. The effect of temperature on fission tracks is well known and is used to determine the thermal history; however, the effect of pressure on the stability of tracks is still under debate. The present work aims to understand the role of pressure on the annealing kinetics of apatite fission tracks. The samples of Durango apatite used in our experiments were chosen for their international recognition as a calibration standard for geological dating. Neutron irradiation of the samples, after total annealing of their spontaneous tracks, produced induced tracks with homogeneous densities and lengths. The effect of pressure associated with temperature on fission track annealing was verified by experimental procedures using a hydraulic press of 1000 t with a toroidal chamber profile. The experiments consisted of a combination of applying 2 and 4 GPa with 20,150,190,235, and 290 °C for 1 and 10 h. The annealing rate was analysed by measuring the lengths of the fission tracks after each experiment using optical microscopy. The results demonstrate that the annealing of apatite fission tracks has a pressure dependence for samples subjected to 2 and 4 GPa. However, when extrapolated to pressures of ⩽150 MPa, compatible with the normal geological context in which apatite fission track methodology is broadly used, this dependence becomes insignificant compared to the temperature effect.

Calcified tissue contains collagen associated with minute crystallites of carbonated apatite. In this study, methods of quantitative X-ray texture analysis were used to determine the orientation distribution and texture strength of apatite in a calcified turkey tendon and in trabecular and cortical regions of osteonal bovine ankle bone (metacarpus). To resolve local heterogeneity, a 2 or 10 microm synchrotron microfocus X-ray beam (lambda = 0.78 A) was employed. Both samples revealed a strong texture. In the case of turkey tendon, 12 times more c axes of hexagonal apatite were parallel to the fibril axis than perpendicular, and a axes had rotational freedom about the c axis. In bovine bone, the orientation density of the c axes was three times higher parallel to the surface of collagen fibrils than perpendicular to it, and there was no preferential alignment with respect to the long axis of the bone (fiber texture). Whereas half of the apatite crystallites were strongly oriented, the remaining half had a random orientation distribution. The synchrotron X-ray texture results were consistent with previous analyses of mineral orientation in calcified tissues by conventional X-ray and neutron diffraction and electron microscopy, but gave, for the first time, a quantitative description. PMID:10221548

Two abandoned lead-zinc mine sites, the Nevada Stewart Mine (NSM) and Success Mine, are located within the Coeur d'Alene Mining District, in northern Idaho. An Apatite II™ Treatment System (ATS) was implemented at each site to treat metal-laden water, mainly zinc. In the ATS, f...

The depletion of calcium in forest ecosystems of the northeastern USA is thought to be a consequence of acidic deposition and to be at present restricting the recovery of forest and aquatic systems now that acidic deposition itself is declining. This depletion of calcium has been inferred from studies showing that sources of calcium in forest ecosystems namely, atmospheric deposition and mineral weathering of silicate rocks such as plagioclase, a calcium-sodium silicate do not match calcium outputs observed in forest streams. It is therefore thought that calcium is being lost from exchangeable and organically bound calcium in forest soils. Here we investigate the sources of calcium in the Hubbard Brook experimental forest, through analysis of calcium and strontium abundances and strontium isotope ratios within various soil, vegetation and hydrological pools. We show that the dissolution of apatite (calcium phosphate) represents a source of calcium that is comparable in size to known inputs from atmospheric sources and silicate weathering. Moreover, apatite-derived calcium was utilized largely by ectomycorrhizal tree species, suggesting that mycorrhizae may weather apatite and absorb the released ions directly, without the ions entering the exchangeable soil pool. Therefore, it seems that apatite weathering can compensate for some of the calcium lost from base-poor ecosystems, and should be considered when estimating soil acidification impacts and calcium cycling. PMID:12066181

A combined experimental and computational approach was employed to investigate the feasibility and effectiveness of characterizing carbonated apatite (CAp) by infrared (IR) spectroscopy. First, an experimental comparative study was conducted to identify characteristic IR vibrational bands of carbonate substitution in the apatite lattice. The IR spectra of pure hydroxyapatite (HA), carbonate adsorbed on the HA surface, a physical mixture of HA and sodium carbonate monohydrate, a physical mixture of HA and calcite, synthetic CAps prepared using three methods (precipitation method, hydrothermal route, and solid-gas reaction at high temperature) and biological apatites (human enamel, human cortical bone, and two animal bones) were compared. Then, the IR vibrational bands of carbonate in CAp were calculated with density functional theory. The experimental study identified characteristic IR bands of carbonate that cannot be generated from surface adsorption or physical mixtures and the results show that the bands at ∼880, 1413, and 1450 cm(-1) should not be used as characteristic bands of CAp since they could result from carbonate adsorbed on the apatite crystals surface or present as a separate phase. The combined experimental and computational study reveals that the carbonate v3 bands at ∼1546 and 1465 cm(-1) are, respectively, the IR signature bands for type A CAp and type B CAp. PMID:23533194

Fluoride substituted apatite cement (fs-AC) was synthesized by using the cement powders of tetracalcium phosphate (TTCP) and sodium fluoride (NaF), and the cement powders were mixed with diluted phosphoric acid (H 3PO 4) as cement liquid to form fs-AC paste. The fs-AC paste could be directly filled into the carious cavities to repair damaged dental enamel. The results indicated that the fs-AC paste was changed into fluorapatite crystals with the atom molar ratio for calcium to phosphorus of 1.66 and the F ion amount of 3 wt% after self-hardening for 2 days. The solubility of fs-AC in Tris-HCl solution (pH 6) was slightly lower than hydroxyapatite cement (HAC) that was similar to the apatite in enamel, indicating the fs-AC was much insensitive to the weakly acidic solution than the apatite in enamel. The fs-AC was tightly combined with the enamel surface because of the chemical reaction between the fs-AC and the apatite in enamel after the caries cavities was filled with fs-AC. The extracts of fs-AC caused no cytotoxicity on L929 cells, which satisfied the relevant criterion on dental biomaterials, revealing good cytocompatibility. The fs-AC had potential prospect for the reconstitution of carious lesion of dental enamel.

Osteoporosis represents a major public health problem and increases patient morbidity through its association with fragility fractures. Among the different treatments proposed, strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk. While the localization of Sr(2+) cations in the bone matrix has been extensively studied, little is known regarding the status of Sr(2+) cations in natural biological apatite. In this investigation the local environment of Sr(2+) cations has been investigated through XANES (X-ray absorption near-edge structure) spectroscopy in a set of pathological and physiological apatites. To assess the localization of Sr(2+) cations in these biological apatites, numerical simulations using the ab initio FEFF9 X-ray spectroscopy program have been performed. The complete set of data show that the XANES part of the absorption spectra may be used as a fingerprint to determine the localization of Sr(2+) cations versus the mineral part of calcifications. More precisely, it appears that a relationship exists between some features present in the XANES part and a Sr(2+)/Ca(2+) substitution process in site (I) of crystal apatite. Regarding the data, further experiments are needed to confirm a possible link between the relationship between the preparation mode of the calcification (cellular activity for physiological calcification and precipitation for the pathological one) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Is it possible to draw a line between life and chemistry through the localization of Sr in apatite? The question is open for discussion. A better structural description of these physiological and pathological calcifications will help to develop specific therapies targeting the demineralization process in the case of osteoporosis. PMID:21997917

Osteoclasts in culture are non-transformed cell types that spontaneously develop specific cell-adhesion devices such as podosomes. An individual podosome is a complex network of filamentous actin (F-actin) unit structure that collectively, with other proteins, self-organizes as the sealing zone. Major matrix degradation on apatite seems to proceed under the ruffled-border domain, which is an enclosed extracellular compartment tightly sealed off by this sealing zone. Presently we found that usually the top of finger-like projections of the ruffled border reached toward the plane of the apatite surface, where a shallow degradation of apatite took place. Simultaneously, we obtained several pieces of structural evidence indicating that a specific protrusion referred to as an invasive podosome (invadopodium), which was continuous with podosomes derived from the sealing zone, invaded deeply into apatite matrix and degraded it. The F-actin architecture of the invasive podosome - an active extracellular matrix-degrading, actin-rich cell protrusion - could be distinguished from that of other punctate F-actin structures including the individual podosome, sealing zone, and ruffled border projection. Invasive podosomes contained 2 different F-actin populations, i.e., an interconnected meshwork and a parallel array of bundles. The morphological variability of these protrusions was apparent, having a single cylindrical to lamella-shaped cytoskeletal organization. Our present observations strongly suggest that the degradation of apatite substrate-resorbing osteoclasts appears to have been preceded by the combined appearance of ruffled border and invasive podosomes, and also occurred simultaneously with cell migration during an alternating cycle of resorption and migration. PMID:27323283

Individual detrital apatite grains from the Esplanade, Coconino, and Moenkopi Formations in the Grand Canyon region of the Colorado Plateau yield (U-Th)/He dates from 104 to 5 Ma. The range of dates within each unit far exceeds analytical uncertainty, but correlates with both He concentration [He] and effective U concentration [eU]. These dates are all significantly younger than the sandstone units, indicating partial to complete He loss following deposition. Recently published laboratory diffusion data suggest that He retentivity in apatite increases with radiation damage. Forward models predict that the consequences of this effect will be manifested most clearly as a correlation between (U-Th)/He dates and the [He] and [eU] in suites of apatites that (1) are characterized by a large span of [eU], and (2) had thermal histories in which sufficient time elapsed for the apatite He diffusion kinetics to diverge prior to reheating and partial resetting. Apatites in the sedimentary units investigated fit these cri teria. Using geologically reasonable deposition, burial, and unroofing histories, simulations that include the effect of radiation damage on apatite He retentivity can reproduce the observed distributions of apatite dates and correlations with parent and daughter concentrations. These results suggest that a span of (U-Th)/He dates positively correlated with [eU] may provide important information regarding a sample's thermal history.

Phosphate groups on materials surfaces are known to contribute to apatite formation upon exposure of the materials in simulated body fluid and improved affinity of the materials for osteoblast-like cells. Typically, polymers containing phosphate groups are organic matrices consisting of apatite-polymer composites prepared by biomimetic process using simulated body fluid. Ca(2+) incorporation into the polymer accelerates apatite formation in simulated body fluid owing because of increase in the supersaturation degree, with respect to apatite in simulated body fluid, owing to Ca(2+) release from the polymer. However, the effects of phosphate content on the Ca(2+) release and apatite-forming abilities of copolymers in simulated body fluid are rather elusive. In this study, a phosphate-containing copolymer prepared from vinylphosphonic acid, 2-hydroxyethyl methacrylate, and triethylene glycol dimethacrylate was examined. The release of Ca(2+) in Tris-NaCl buffer and simulated body fluid increased as the additive amount of vinylphosphonic acid increased. However, apatite formation was suppressed as the phosphate groups content increased despite the enhanced release of Ca(2+) from the polymer. This phenomenon was reflected by changes in the surface zeta potential. Thus, it was concluded that the apatite-forming ability of vinylphosphonic acid-2-hydroxyethyl methacrylate-triethylene glycol dimethacrylate copolymer treated with CaCl2 solution was governed by surface state rather than Ca(2+) release in simulated body fluid. PMID:27585911

Ground water at the Fry Canyon, Utah site (pH 7; 4.8 mM alkalinity) is contaminated with uranium (to 20 mg/L) leached from tailings at a now-abandoned ore upgrader facility. An apatite-based chemical reactive barrier (PRB) was installed in the hydrologic flow path at Fry Canyon in 1997 to determine its technological and economic feasibility for ground water remediation. As part of this study, uranium (U(VI)) was reacted with apatite materials, evaluated for use in the PRB, under laboratory conditions. The speciation of U(VI) was subsequently characterized by EXAFS spectroscopy. U(VI) speciation in pelletized bone charcoal apatite recovered from the PRB was also characterized. In carbonate-containing solutions and in ground water, uranium was found to be adsorbed to the apatite materials as apatite-uranyl-carbonate (i.e., "ternary") surface complexes. In carbonate-free solutions, apatite-uranyl-phosphate ternary complexes were found to predominate. At high total uranium concentrations, uranium solubility was limited by precipitation of the uranyl phosphate phase, chernikovite. Uranium solubility was significantly enhanced in the presence of dissolved carbonate. In an apatite-based PRB application, close monitoring will be required to ensure that U(VI) breakthrough does not occur when adsorption equilibrium is reached. The sorptive capacity of the PRB will be affected by the dissolved carbonate concentration of the ground water.

An assemblage of magnetite and apatite is common worldwide in different ore deposit types, including disparate members of the iron-oxide copper-gold (IOCG) clan. The Kiruna-type iron oxide-apatite deposits, a subtype of the IOCG family, are recognized as economic targets as well. A wide range of competing genetic models exists for magnetite-apatite deposits, including magmatic, magmatic-hydrothermal, hydrothermal(-metasomatic), and sedimentary(-exhalative). The sources and mechanisms of transport and deposition of Fe and P remain highly debatable. This study reports petrographic and geochemical features of the magnetite-apatite-rich vein assemblages in the dolerite dykes of the Gairdner Dyke Swarm (~0.82 Ga) that intruded the Roxby Downs Granite (~0.59 Ga), the host of the supergiant Olympic Dam IOCG deposit. These symmetrical, only few mm narrow veins are prevalent in such dykes and comprise besides usually colloform magnetite and prismatic apatite also further minerals (e.g., calcite, quartz). The genetic relationships between the veins and host dolerite are implied based on alteration in the immediate vicinity (~4 mm) of the veins. In particular, Ti-magnetite-ilmenite is partially to completely transformed to titanite and magmatic apatite disappears. We conclude that the mafic dykes were a local source of Fe and P re-concentrated in the magnetite-apatite veins. Uranium-Pb ages for vein apatite and titanite associated with the vein in this case study suggest that alteration of the dolerite and healing of the fractures occurred shortly after dyke emplacement. We propose that in this particular case the origin of the magnetite-apatite assemblage is clearly related to hydrothermal alteration of the host mafic magmatic rocks.

Synthetic tin(II)apatite reduces pertechnetate from the mobile +7 to a non-mobile oxidation state and sequesters the technetium, preventing re-oxidization to mobile +7 state under acidic or oxygenated conditions. Previous work indicated technetium reacted Sn(II)apatite can achieve an ANSI leachability index of 12.8 in Cast Stone. An effect by pH is observed on the distribution coefficient, the highest distribution coefficient being l70,900 observed at pH levels of 2.5 to 10.2. The tin apatite was resistant to releasing technetium under test conditions.

The apatite (U-Th)/He (AHe) system has rapidly become a very popular thermochronometer to constrain exhumation and relief evolution in a variety of geological contexts, as it allows dating and estimating the amount of denudation. However, the interpretation of AHe data depends on a precise knowledge of He diffusion in apatite, which is sensible in the 55 to 120°C range. Several studies suggest that radiation damage generated by U and Th decay can create traps for He atoms, increasing He retention as a function of the number of traps. The radiation damage also anneals with temperature and the amount of damage in an apatite crystal will be a balance between production and annealing, controlled by U-Th concentration, grain chemistry and thermal history (Shuster et al., 2006; Flowers et al., 2009; Gautheron et al., 2009; 2013). However these models are not well constrained and do not fully explain the mechanism of He retention. In order to have a deeper insight on this issue, multidisciplinary studies on apatite combining diffusion experiments by Elastic Recoil Diffusion Analysis (ERDA) with diffusion calculation Density Functional Theory (DFT) were performed. ERDA experiments were conducted on different macro-crystals, and we probed the shape of a He profile implanted into a planar and polished surface of the crystal. The helium profile evolves with temperature and allows the quantification of He diffusivity. Additionally, DFT calculations of a crystal of apatite have been run to find the favored paths of a helium atom between interstitial sites, leading to a computation of the activation energy and the diffusion coefficient. Crystals with different F and Cl compositions, in similar proportion as natural ones, have been investigated and show chemical variations due to steric effects. Using ERDA and DFT approaches, we demonstrate that in addition to the damage, the grain chemistry strongly impacts He diffusivity and needs to be taken into account. Shuster, D., Flowers

The Precambrian-Cambrian transition forms one of the most dramatic time periods in Earth's history, as global changes in tectonics, climate and chemistry in the atmosphere and oceans favoured the worldwide Cambrian Radiation and a concomitant ecosphere revolution. This time interval is paralleled by the first appearance of the widespread giant phosphorites. The well-known Meishucun section (South China), a former candidate section for the Pc-C boundary, documents phosphorite genesis amongst a rapid biodiversification, immediately following the end of the Precambrian in a low-latitude, shallow-water carbonate shelf. This contribution aims to elucidate the relation between simultaneous phosphorite deposition and global environmental conditions at the Pc-C boundary by using stable carbon and oxygen isotope analyses. Accurate determinations of d13C and d18O values may allow conclusions about ancient ocean circulation, paleo-productivity, paleo-temperatures, and most prominently diagenetic processes. The investigated samples from the Meishucun section basically consist of apatite, dolomite, and quartz that may be further devided into a lower and upper phosphorite as well as an overlying dolostone intervall. Additionally, calcite and siderite occur as minor compounds in some samples. Bulk d13C values of the carbonate fraction correlate with dolomite abundance throughout the section ranging from -4 to 1 per mil. Furthermore, several horizons suggest a relation between d13C values and apatite content, implying lower d13C values in apatites compared to coexisting dolomite. A slight negative d13C excursion at the top of the lower phosphorite coincides with the first appearance of small shelly fossils. Corresponding bulk d18O values generally show a stratigraphic-upward trend towards lower values throughout the record with slightly higher values in dolomite-rich sections. This may either indicate a warming trend during deposition, an isotopic shift in sea water composition

This effort is part of the technetium management initiative and provides data for the handling and disposition of technetium. To that end, the objective of this effort was to challenge tin(II)apatite (Sn(II)apatite) against double-shell tank 241-AN-105 simulant spiked with pertechnetate (TcO{sub 4}{sup -}). The Sn(II)apatite used in this effort was synthesized on site using a recipe developed at and provided by Sandia National Laboratories; the synthesis provides a high quality product while requiring minimal laboratory effort. The Sn(II)apatite reduces pertechnetate from the mobile +7 oxidation state to the non-mobile +4 oxidation state. It also sequesters the technetium and does not allow for re-oxidization to the mo bile +7 state under acidic or oxygenated conditions within the tested period oftime (6 weeks). Previous work (RPP-RPT-39195, Assessment of Technetium Leachability in Cement-Stabilized Basin 43 Groundwater Brine) indicated that the Sn(II)apatite can achieve an ANSI leachability index in Cast Stone of 12.8. The technetium distribution coefficient for Sn(II)apatite exhibits a direct correlation with the pH of the contaminated media. Table A shows Sn(II)apatite distribution coefficients as a function of pH. The asterisked numbers indicate that the lower detection limit of the analytical instrument was used to calculate the distribution coefficient as the concentration of technetium left in solution was less than the detection limit. The loaded sample (200 mg of Sn(II)apatite loaded with O.311 mg of Tc-99) was subjected to different molarities of nitric acid to determine if the Sn(II)apatite would release the sequestered technetium. The acid was allowed to contact for 1 minute with gentle shaking ('1st wash'); the aqueous solution was then filtered, and the filtrate was analyzed for Tc-99. Table B shows the results ofthe nitric acid exposure. Another portion of acid was added, shaken for a minute, and filtered ('2nd wash'). The technetium-loaded Sn(II)apatite

The aim of this work is to perform such a chemical modification of the implant that in vivo conditions on its surface, heterogeneous nucleation of apatite from the body fluid could be easily induced and then its growth successfully performed. The laboratory experiments were carried out with carbon-carbon biocomposites and carbon needled clothes. The surface of carbon was coated with the sol-gel silica or calcium silicate layer and then, under physiological conditions, thermostatically soaked in the synthetic or natural body fluid. Successive steps of the apatite growth were monitored by infrared spectroscopy. It was found that the nucleation and growth of carbonate containing apatite took place at the surface and was more effective on silica-calcium than on silica substrate. The natural body fluid, compared with synthetic body fluid much enhanced the apatite precipitation. This observation supports suggestion that also proteins can act as nucleation centres.

We report H and C contents and δD and δ 13C values of apatites from 15 alkaline intrusive complexes ranging in age from 110 Ma to 2.6 Ga. Sampling focused on carbonatites, but included silicate rocks as well. Heating at temperatures up to 1500°C is needed to extract fully H 2O and CO 2 from these apatites. Apatites from carbonatite-rich intrusive complexes contain 0.2-1.1 wt% H 2O and 0.05-0.70 wt% CO 2; apatites from two silicate-rich alkaline complexes with little or no carbonatite are generally poorer in both volatile components (0.1-0.2% H 2O and 0.01-0.11% CO 2). D/H ratios in apatites from these rocks are bimodally distributed: group I (δD = -51 to -74‰) and group II (δD = -88 to -104‰). We suggest that the δD values of group I apatites represent primitive, mantle-derived values and that the group II apatites crystallized from degassed magmas, resulting in lower H 2O contents and δD values. Although many factors influence the extent of degassing, the depth of emplacement could represent a major control. In contrast to H 2O contents and δD values, CO 2 contents and δ 13C values of gas released at high temperatures from multiple aliquots of these apatite samples are variable. This suggests the presence of more than one C-bearing component in these apatites, one of which is proposed to be dissolved carbonate; the other, with δ 13C ˜apatites have δD values similar to those of primitive, mantle-derived basaltic magmas and overlap with (but cover a narrower range than) mantle-derived mica, amphibole, and whole rocks. δ 13C values also overlap typical upper mantle. These results suggest that igneous apatites can retain their primary δD and δ 13C values.

We have investigated the applicability of a simple and inexpensive osteoclastic assay system using bone-like apatite-coated polyethyleneterephthalate (PET) disks. A 1 microm thick apatite layer, uniform and homogeneous bone-mineral-like with no organic components, was made on PET disks using a biomimetic process. As substrates for an osteoclastic assay, these coated disks were compared with dentine as well as with bone-like or heat-treated apatite of various thicknesses on apatite- and wollastonite-containing glass ceramic (A-W GC) disks. The unfractionated bone cells, including osteoclasts, of a neonatal rabbit were seeded onto these substrates. By scanning electron microscopic examination, the resorption lacunae of the thick bone-like apatite clearly showed track-like shapes at various depths, similar to those of dentine although the border between the A-W GC and the apatite was unclear. In contrast, those of heat-treated apatite showed small and shallow shapes with irregular margins, quite different from those of dentine. By reducing the thickness of bone-like apatite to 1 microm as well as using PET as its substrate, the margins of the resorption lacunae became quite clear, and with the use of phase-contrast microscopy during culture, osteoclasts and resorption pits could be precisely observed. The resorbed area, easily measured with the aid of bright-field microscopy and an image analyzer, was found to have increased in a time-dependent manner and at the end of 4 days of culture was not statistically different from that of dentine. PMID:9773824

Apatite is capable of incorporating all major magmatic volatile species (H2O, CO2, S, Cl and F) into its crystal structure. Analysis of apatite volatile contents can be related to parental magma compositions through the application of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994). Once included within phenocrysts, apatite inclusions are isolated from the melt and preserve a temporal record of magmatic volatile contents in the build-up to eruption. In this work, we measured the volatile compositions of apatite inclusions, apatite microphenocrysts and pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy (Stock et al. 2016). These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to decipher pre-eruptive magmatic processes. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset at shallow levels during ascent. Given the high diffusivity of volatiles in apatite (Brenan, 1993), the preservation of volatile-undersaturated melt compositions in microphenocrysts suggests that saturation was only achieved 10 - 103 days before eruption. We suggest that late-stage transition into a volatile-saturated state caused an increase in magma chamber overpressure, which ultimately triggered the Astroni 1 eruption. This has major implications for monitoring of Campi Flegrei and other similar volcanic systems. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Stock et al., 2016, Nat. Geosci. Gualda et al., 2012. J. Pet., 53, 875

The effect of disodium EDTA, as an additive, on the crystallization of struvite and carbonate apatite was studied. The growth of struvite crystals and carbonate apatite occurred in the solution of artificial urine at 37 °C and at the condition emulating real urinary tract infection. The results demonstrate that the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). The struvite crystal mean and median diameters were found to decrease in the presence of disodium EDTA but the crystal morphology and habit remain almost unchanged. Disodium EDTA has demonstrated its potential to be further investigated in the presence of bacteria and in vivo conditions.

Titanium and its alloys are currently the mainly used materials to manufacture orthopaedic implants due to their excellent mechanical properties and corrosion resistance. Although these materials are bioinert, the improvement of biological properties (e.g., bone implant contact) can be obtained by the application of a material that mimics the bone extracellular matrix. To this aim, this work describes a new method to produce nanostructured collagen-apatite composites on titanium alloy substrate, by combining electrospinning and biomimetic mineralization. The characterization results showed that the obtained mineralized scaffolds have morphological, structural, and chemical compositional features similar to natural bone extracellular matrix. Finally, the topographic distribution of the chemical composition in the mineralized matrix evaluated by Fourier Transform Infrared microspectroscopy demonstrated that the apatite nanocrystals cover the collagen fibers assembled by the electrospinning. PMID:22400013

The Grand Canyon is one of the most dramatic features on Earth, yet when and why it was carved have been controversial topics for more than 150 years. Here, we present apatite (4)He/(3)He thermochronometry data from the Grand Canyon basement that tightly constrain the near-surface cooling history associated with canyon incision. (4)He/(3)He spectra for eastern Grand Canyon apatites of differing He date, radiation damage, and U-Th zonation yield a self-consistent cooling history that substantially validates the He diffusion kinetic model applied here. Similar data for the western Grand Canyon provide evidence that it was excavated to within a few hundred meters of modern depths by ~70 million years ago (Ma), in contrast to the conventional model in which the entire canyon was carved since 5 to 6 Ma. PMID:23196906

The Grand Canyon is one of the most dramatic features on Earth, yet when and why it was carved have been controversial topics for more than 150 years. Here, we present apatite 4He/3He thermochronometry data from the Grand Canyon basement that tightly constrain the near-surface cooling history associated with canyon incision. 4He/3He spectra for eastern Grand Canyon apatites of differing He date, radiation damage, and U-Th zonation yield a self-consistent cooling history that substantially validates the He diffusion kinetic model applied here. Similar data for the western Grand Canyon provide evidence that it was excavated to within a few hundred meters of modern depths by ~70 million years ago (Ma), in contrast to the conventional model in which the entire canyon was carved since 5 to 6 Ma.

In this study, a degradable, hierarchically porous silica/apatite composite material is developed from a simple low-temperature synthesis. Mesoporosity is induced in the silica portion by the use of supramolecular templating. The template is further removed by calcination. Firstly, hydroxyapatite is synthesized through a sol-gel method at near room temperature conditions. After the mineralization process, the crystal surface is coated with a mesoporous silica matrix using the templates already present in the bulk solution. The material is characterized by XRD, N(2)-sorption, FT-IR, SEM/EDS, and TEM. The coating layer is distributed fairly homogeneously over the apatite surface and the coating thickness is easily adjustable and dependent on the amount of added silica precursor. The hybrid material is shown to efficiently induce calcium phosphate formation under in vitro conditions and simultaneously work as a carrier system for drugs. PMID:15993485

Geological and mineralogical evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonatefluorapatite is dissolved in 1.5 M orthophosphoric acid at a temperature of 5??C or slightly below and fluorapatite is dissolved in cold 1.2 M hydrochloric acid (approximately 5??C) containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium(IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments. ?? 1958.

The apatite group of minerals is a family of calcium phosphate phases. Apatite is the principal component of bone tissue, and it also occurs naturally as mineral deposits in the geosphere. Bone char is calcined (coked) animal bone, containing activated carbon as well as calcium phosphate mineral phases. Apatite II{trademark} is a more reactive form of apatite, supplied by UFA Ventures, Inc., at a cost of approximately 1/4 that of commercial bone char. Apatite is shown to be effective for the removal of select heavy metal impurities in groundwater. Previous investigations have demonstrated that apatite is an effective medium for the stabilization of soluble lead, cadmium, and zinc from mine waste leachate by the formation of highly insoluble precipitate phases. The performance of bone char and apatite II are compared with other candidate sorption media (including granular activated carbon and anion exchange resin) for the removal of soluble uranyl ion in synthetic DOE Site groundwater supplemented with varying levels of interfering nitrate ion. Apatite II has a greater affinity for U(VI), especially in the presence of nitrate ion, as evidenced by a larger value for the conditional distribution coefficient (Kd) in batch test experiments. Contact of uranyl nitrate solution with apatite II is shown to produce highly insoluble mineral phases of the autunite group (calcium uranyl phosphate hydrates). Apatite II is also demonstrated to be moderately effective for the removal of soluble radioactive isotopes of strontium, but not cesium, when these ions are supplemented into authentic DOE Site groundwater.

The oxynitridation of biomedical titanium metal under a precisely regulated oxygen partial pressure (PO2) of 10(-14)Pa in nitrogen atmosphere at 973 K for 1 h strongly enhanced apatite formation compared with that on Ti heated in air. The factors governing the high apatite-forming ability are discussed from the viewpoint of the surface properties of Ti heated under a PO2 of 10(-14)Pa in nitrogen atmosphere determined from X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. Nitrogen (N)-doped TiO2 (interstitial N) was formed on pure Ti heated under a PO2 of 10(-14)Pa in nitrogen atmosphere at 973 K. The XPS O1s main peak shifted toward a lower binding energy upon heating under a PO2 of 10(-14)Pa. This shift may be due to the formation of oxygen vacancies. This Ti surface had a positive zeta potential of approximately 20 mV. According to time-of-flight secondary ion mass spectroscopy results, PO4(3-) ions were predominantly adsorbed on Ti soaked in simulated body fluid (SBF) after heat treatment, followed by calcium ions. It was concluded that the apatite formation kinetics can be described using the Avrami-Erofeev equation with an Avrami index of n=2, which implies the instantaneous nucleation of apatite on the surface of Ti soaked in SBF after heat treatment at 973 K under a PO2 of 10(-14)Pa. PMID:23910327

We demonstrate, for the first time, that the (Fe0.75B0.15Si0.1)100-xNbx (x=0, 1 and 3at.%) metallic glasses without toxic and allergic elements exhibit excellent apatite-forming ability in simulated body fluids (SBF), which is expected to be a new generation of biomaterials in stents and orthopedic implants. For the alloys without any surface treatment, spherical particles corresponding to octacalcium phosphate are spontaneously nucleated and precipitated throughout the alloy surface after immersion only for 1day, indicating that the present alloys possess an unusual high bioactivity. During the subsequent in-vitro immersion for 3days, SEM image reveals the typical 'cauliflower' morphology of bone-like hydroxyapatite (HA) with Ca/P ratio of 1.65. In addition, it is surprising to find that the in-vitro SBF immersion not only leads to the formation and growth of the apatite layer but also causes the progressive development of the underlying alloy substrate. Moreover, for the alloys immersed for 3 or 9days, the substrate alloy just beneath the apatite layer consists of a hierarchical nano/macro-porous structure through selective dissolution of the active components Fe and B in the surface. XPS analysis indicates that the apatite nucleation on the present alloys in SBF is attributed to the specific dissolution properties of the present alloys and the fast formation of Si-OH and Fe-OH or Nb-OH functional groups, followed by combination of these groups with Ca(2+) and phosphate ions. PMID:27612742

An injectable permeable reactive barrier (PRB) technology was developed to sequester 90Sr in groundwater through the in situ formation of calcium-phosphate mineral phases, specifically apatite that incorporates 90Sr into the chemical structure. An integrated, multi-scale development and testing approach was used that included laboratory bench-scale experiments, an initial pilot-scale field test, and the emplacement and evaluation of a 300-ft-long treatability-test-scale PRB. Standard groundwater wells were used for emplacement of the treatment zone, allowing treatment of contaminants too deep below ground surface for trench-and-fill type PRB technologies. The apatite amendment formulation uses two separate precursor solutions, one containing a Ca-citrate complex and the other a Na-phosphate solution, to form apatite precipitate in situ. Citrate is needed to keep calcium in solution long enough to achieve a more uniform and areally extensive distribution of precipitate formation. In the summer of 2008, the apatite PRB technology was applied as a 91-m (300-ft) -long permeable reactive barrier on the downgradient edge of a 90Sr plume beneath the Hanford Site in Washington State. The technology was deployed to reduce 90Sr flux discharging to the Columbia River. Performance assessment monitoring data collected to date indicate the barrier is meeting performance objectives. The average reduction in 90Sr concentrations at four downgradient compliance monitoring locations was 95% relative to the high end of the baseline range approximately 1 year after treatment, and continues to meet remedial objectives more than 4 years after treatment.

Metal removal from contaminated effluents was examined following reaction with natural apatites of biological and geological origin or a synthetic hydroxylapatite (HAP). Mammalian meat and bone meal (MBM), a by-product from meat industry, was the biological apatite source. The effect of incineration on metal removal capacity of MBM and HAP was also examined. The reactivity of apatites for all tested metals (Pb, Cd, Cu and Zn) followed the general order: synthetic > biological > mineral. For all apatites tested, Pb was removed best and preferentially from multi-metal solutions. MBM and HAP (0.5 g solid) removed Pb completely from both highly concentrated single metal solutions (50 ml, 1000 mg/L Pb) and from multi-metal solutions (50 ml) with 100 mg/L each of Cd, Cu and Zn in addition to Pb. The incineration of MBM (725 degrees C and 850 degrees C) reduced significantly its capacity for removal of Zn (by 47%, from 56 mg/g to 9 mg/g) and Cd (by 38%, from 53 mg/g to 13 mg/g) in particular and to a lesser extent for Cu (by 14%, from 61 mg/g to 46 mg/g) while the removal of Pb was not affected (100 mg/g). The same pattern was observed for incinerated HAP. SEM and XRD analysis indicated that HAP reacted with the metals by precipitation of pure metal phosphates--Pb hydroxylapatite, Zn phosphate (hopeite), a Cd phosphate (identified only by ED-SEM) and Cu phosphate (libenthenite). PMID:19187953

A novel method to coat electrospun poly(D,L-lactic-co-glycolic acid) (PLGA) fiber surfaces evenly and efficiently with low-crystalline carbonate apatite crystals using a poly(vinyl alcohol) (PVA) vehicle system carrying calcium ions was presented. A non-woven PLGA fabric was prepared by electrospinning: a 10 wt% PLGA solution was prepared using 1,1,3,3-hexafluoro-2-propanol as a solvent and electrospun under a electrical field of 1 kV/cm using a syringe pump with a flowing rate of 3 ml/h. The non-woven PLGA fabric, 12 mm in diameter and 1 mm in thickness, was cut and then coated with a PVA solution containing calcium chloride dihydrate (specimen PPC). As controls, pure non-woven PLGA fabric (specimen P) and fabric coated with a calcium chloride dihydrate solution without PVA (specimen PC) were also prepared. Three specimens were exposed to simulated body fluid for 1 week and this exposure led to form uniform and complete apatite coating layer on the fiber surfaces of specimen PPC. However, no apatite had formed to the fiber surfaces of specimen P and only inhomogeneous coating occurred on the fiber surfaces of specimen PC. These results were explained in terms of the calcium chelating and adhesive properties of PVA vehicle system. The practical implication of the results is that this method provides a simple but efficient technique for coating the fiber surface of an initially non-bioactive material with low-crystalline carbonate apatite. PMID:20507712

The purpose of this study is to evaluate emplacement of phosphate into subsurface sediments in the Hanford Site 100-N Area by two different technologies: groundwater injection of a Ca-citrate-PO4 solution and water-jet injection of sodium phosphate and/or fish-bone apatite. In situ emplacement of phosphate and apatite adsorbs, then incorporates Sr-90 into the apatite structure by substitution for calcium. Overall, both technologies (groundwater injection of Ca-citrate-PO4) and water-jet injection of sodium phosphate/fish-bone apatite) delivered sufficient phosphate to subsur¬face sediments in the 100-N Area. Over years to decades, additional Sr-90 will incorporate into the apatite precipitate. Therefore, high pressure water jetting is a viable technology to emplace phosphate or apatite in shallow subsurface sediments difficult to emplace by Ca-citrate-PO4 groundwater injections, but further analysis is needed to quantify the relevant areal extent of phosphate deposition (in the 5- to 15-ft distance from injection points) and cause of the high deposition in finer grained sediments.

A plasma- and precursor-assisted biomimetic process utilizing plasma and alternate dipping treatments was applied to a Leed-Keio artificial ligament to produce a thin coating of apatite in a supersaturated calcium phosphate solution. Following plasma surface modification, the specimen was alternately dipped in calcium and phosphate ion solutions three times (alternate dipping treatment) to create a precoating containing amorphous calcium phosphate (ACP) which is an apatite precursor. To grow an apatite layer on the ACP precoating, the ACP-precoated specimen was immersed for 24 h in a simulated body fluid with ion concentrations approximately equal to those in human blood plasma. The plasma surface modification was necessary to create an adequate apatite coating and to improve the coating adhesion depending on the plasma power density. The apatite coating prepared using the optimized conditions formed a thin-film that covered the entire surface of the artificial ligament. The resulting apatite-coated artificial ligament should exhibit improved osseointegration within the bone tunnel and possesses great potential for use in ligament reconstructions. PMID:24048251

Chitosan/biomimetic apatite thin films were grown in mild conditions of temperature and pressure by Combinatorial Matrix-Assisted Pulsed Laser Evaporation on Ti, Si or glass substrates. Compositional gradients were obtained by simultaneous laser vaporization of the two distinct material targets. A KrF* excimer (λ=248nm, τFWHM=25ns) laser source was used in all experiments. The nature and surface composition of deposited materials and the spatial distribution of constituents were studied by SEM, EDS, AFM, GIXRD, FTIR, micro-Raman, and XPS. The antimicrobial efficiency of the chitosan/biomimetic apatite layers against Staphylococcus aureus and Escherichia coli strains was interrogated by viable cell count assay. The obtained thin films were XRD amorphous and exhibited a morphology characteristic to the laser deposited structures composed of nanometric round shaped grains. The surface roughness has progressively increased with chitosan concentration. FTIR, EDS and XPS analyses indicated that the composition of the BmAp-CHT C-MAPLE composite films gradually modified from pure apatite to chitosan. The bioevaluation tests indicated that S. aureus biofilm is more susceptible to the action of chitosan-rich areas of the films, whilst the E. coli biofilm proved more sensible to areas containing less chitosan. The best compromise should therefore go, in our opinion, to zones with intermediate-to-high chitosan concentration which can assure a large spectrum of antimicrobial protection concomitantly with a significant enhancement of osseointegration, favored by the presence of biomimetic hydroxyapatite. PMID:27418570

Crystallization from amorphous phases is an emerging pathway for making advanced materials. Biology has made use of amorphous precursor phases for eons and used them to produce structures with remarkable properties. Herein, we show how the design of the amorphous phase greatly influences the nanocrystals formed therefrom. We investigate the transformation of mixed amorphous calcium phosphate/amorphous calcium carbonate phases into bone-like nanocrystalline apatite using in situ synchrotron X-ray diffraction and IR spectroscopy. The speciation of phosphate was controlled by pH to favor HPO4 (2-) . In a carbonate free system, the reaction produces anisotropic apatite crystallites with large aspect ratios. The first formed crystallites are highly calcium deficient and hydrogen phosphate rich, consistent with thin octacalcium phosphate (OCP)-like needles. During growth, the crystallites become increasingly stoichiometric, which indicates that the crystallites grow through addition of near-stoichiometric apatite to the OCP-like initial crystals through a process that involves either crystallite fusion/aggregation or Ostwald ripening. The mixed amorphous phases were found to be more stable against phase transformations, hence, the crystallization was inhibited. The resulting crystallites were smaller and less anisotropic. This is rationalized by the idea that a local phosphate-depletion zone formed around the growing crystal until it was surrounded by amorphous calcium carbonate, which stopped the crystallization. PMID:27460160

A series of doped apatites have been deposited onto titanium (V) substrates using a novel ambient temperature blasting process. The potential of these deposited doped apatites as non-colonizing osteoconductive coatings has been evaluated in vitro. XPS, EDX, and gravimetric analysis demonstrated that a high degree of coating incorporation was observed for each material. The modified surfaces were found to produce osteoblast proliferation comparable to, or better than, a hydroxyapatite finish. Promising levels of initial microbial inhibition were observed from the Sr- and Ag-doped surfaces, with the strontium showing prolonged ability to reduce bacteria numbers over a 30-day period. Ion elution profiles have been characterized and linked to the microbial response and based on the results obtained, mechanisms of kill have been suggested. In this study, the direct contact of coated substrate surfaces with microbes was observed to be a significant contributing factor to the antimicrobial performance and the anticolonizing activity. The silver substituted apatite was observed to out-perform both the SrA and ZnA in terms of biofilm inhibition. PMID:20737556

In this study, a phosphorylation treatment of porous anodic alumina (PAA) was performed by wet impregnation in phosphoric acid and a subsequent heat treatment. The PAA and phosphorylated PAA specimens were analyzed using a field emission scanning electron microscope, an energy-dispersive X-ray spectrometer, and Fourier transform infrared spectroscopy. The apatite-forming ability of the phosphorylated PAA was evaluated by soaking the specimens in simulated body fluid for 1, 3, and 7 days. The surface microstructures and chemical property changes after soaking in simulated body fluid were again characterized by field emission scanning electron microscope, energy-dispersive X-ray spectrometer, and Fourier transform infrared spectroscopy. Results of this study demonstrated that the functional -PO4 groups introduced onto the PAA surface dramatically promoted the deposition of bone-like apatite on PAA. The results from this study indicated that the phosphorylation treatment of anodic alumina is an effective method for inducing bone-like apatite formation, and this phosphorylated PAA can be a promising candidate to be used as bioactive surface coatings on implant metals and alloys for orthopedic and dental applications. PMID:24598060

Some soluble phosphate salts, heavily used in agriculture as highly effective phosphorus (P) fertilizers, cause surface water eutrophication, while solid phosphates are less effective in supplying the nutrient P. In contrast, synthetic apatite nanoparticles could hypothetically supply sufficient P nutrients to crops but with less mobility in the environment and with less bioavailable P to algae in comparison to the soluble counterparts. Thus, a greenhouse experiment was conducted to assess the fertilizing effect of synthetic apatite nanoparticles on soybean (Glycine max). The particles, prepared using one-step wet chemical method, were spherical in shape with diameters of 15.8 ± 7.4 nm and the chemical composition was pure hydroxyapatite. The data show that application of the nanoparticles increased the growth rate and seed yield by 32.6% and 20.4%, respectively, compared to those of soybeans treated with a regular P fertilizer (Ca(H2PO4)2). Biomass productions were enhanced by 18.2% (above-ground) and 41.2% (below-ground). Using apatite nanoparticles as a new class of P fertilizer can potentially enhance agronomical yield and reduce risks of water eutrophication. PMID:25023201

Poly(etheretherketone) (PEEK) is a rigid semi-crystalline polymer with outstanding mechanical properties, bone-like stiffness and suitable biocompatibility that has attracted much interest as a biomaterial for orthopedic and dental implants. However, the bio-inert surface of PEEK limits its biomedical applications when direct osteointegration between the implants and the host tissue is desired. In this work, -PO4H2, -COOH and -OH groups were introduced on the PEEK surface by further chemical treatments of the vinyl-terminated silanization layers formed on the hydroxylation-pretreated PEEK surface. Both the surface-functionalized and pristine specimens were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and water contact angle measurements. When placed in 1.5 strength simulated body fluid (SBF) solution, apatite was observed to form uniformly on the functionalized PEEK surface and firmly attach to the substrate. The characterized results demonstrated that the coating was constituted by poorly crystallized bone-like apatite and the effect of surface functional groups on coating formation was also discussed in detail. In addition, in vitro biocompatibility of PEEK, in terms of pre-osteoblast cell (MC3T3-E1) attachment, spreading and proliferation, was remarkably enhanced by the bone-like apatite coating. Thus, this study provides a method to enhance the bioactivity of PEEK and expand its applications in orthopedic and dental implants. PMID:26117784

Two kinds of natural apatite minerals were obtained from two different phosphate deposits in northern China, FanShan, Hebei province and HeiYingShan, Inner Mongolia province. Their chemical compositions, phase structure, and cathodoluminescence (CL) have been comparatively investigated. X-ray diffraction (XRD) analysis indicated that the raw phosphate minerals from FanShan mainly are composed of FanShan apatite (FA) and FanShan mica, respectively, while the ore sample from HeiYingShan contained HeiYingshan apatite (HA) and HeiYingshan magnetite. The mineralogical characteristics and crystal structure of FA and HA were further determined by XRD, scanning electron microscopy, x-ray fluorescence spectrometer, and inductively coupled plasma-mass spectrometry, respectively. These results indicate that FA belongs to fluorapatite, while the HA belongs to hydroxyapatite. The existence of some trace elements has also been verified by the measured CL spectrum. The origin of the observed CL peaks has been discussed, and the relationship of the CL and the chemical composition has also been investigated.

Porous NiTi shape memory alloy (SMA) with 48% porosity and an average pore size of 50-800 μm was synthesized by capsule-free hot isostatic pressing (CF-HIP). To enhance the surface bioactivity, the porous NiTi SMA was subjected to H2O2 and subsequent NaOH treatment. Scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses revealed that a porous sodium titanate (Na2TiO3) film had formed on the surface of the porous NiTi SMA. An apatite layer was deposited on this film after immersion in simulated body fluid at 37°C, while no apatite could be found on the surface of the untreated porous NiTi SMA. The formation of the apatite layer infers that the bioactivity of the porous NiTi SMA may be enhanced by surface chemical treatment, which is favorable for its application as bone implants.

Apatite and zircon separates from the Fish Canyon Tuff (K-Ar age, 27.9??0.7 Myr), San Juan Mtns., Colorado, have been given to over 50 laboratories for fission-track dating. Nineteen laboratories have reported fission-track ages that they have determined for apatites. Nine laboratories have reported their analysis of the zircons. The principal difference between the results reported by the laboratories reflects their choice of the decay constant. The laboratories which use a value of ??f ??? 7.0 ?? 10-17 yr-1 for the spontaneous-fission decay constant of 238U, report an average age for the apatite of 28.5??0.7 Myr, and those using ??f ??? = 8.4 ?? 10-17 yr-1 report an average age of 23.6??1.0 Myr. The average fission-track age for the zircons is 28.4??0.7 Myr. Only laboratories which use ??f ??? 7.0 ?? 10-17 yr-1 reported zircon data. ?? 1981.

Some soluble phosphate salts, heavily used in agriculture as highly effective phosphorus (P) fertilizers, cause surface water eutrophication, while solid phosphates are less effective in supplying the nutrient P. In contrast, synthetic apatite nanoparticles could hypothetically supply sufficient P nutrients to crops but with less mobility in the environment and with less bioavailable P to algae in comparison to the soluble counterparts. Thus, a greenhouse experiment was conducted to assess the fertilizing effect of synthetic apatite nanoparticles on soybean (Glycine max). The particles, prepared using one-step wet chemical method, were spherical in shape with diameters of 15.8 +/- 7.4 nm and the chemical composition was pure hydroxyapatite. The data show that application of the nanoparticles increased the growth rate and seed yield by 32.6% and 20.4%, respectively, compared to those of soybeans treated with a regular P fertilizer (Ca(H2PO4)2). Biomass productions were enhanced by 18.2% (above-ground) and 41.2% (below-ground). Using apatite nanoparticles as a new class of P fertilizer can potentially enhance agronomical yield and reduce risks of water eutrophication.

The bone integration of implants is a complex process which depends on chemical composition and surface morphology. To accelerate osteointegration, metal implants are coated with porous metal or apatites which have been reported to increase mineralisation, improving prosthesis fixation. To study the influence of composition and morphology on the in vivo bioactivity, titanium screws coated by Plasma Flame Spraying (PFS) with titanium or fluorinated apatite (K690) were implanted in sheep tibia and femur for 10 weeks and studied by micro-Raman and IR spectroscopy. The same techniques, together with thermogravimetry, were used for characterising the pre-coating K690 powder. Contrary to the manufacturer report, the K690 pre-coating revealed to be composed of a partially fluorinated apatite containing impurities of Ca(OH) 2 and CaCO 3. By effect of PFS, the impurities were decomposed and the crystallinity degree of the coating was found to decrease. The vibrational spectra recorded on the implanted screws revealed the presence of newly formed bone; for the K690-coated screws at least, a high level of osteointegration was evidenced.

Remineralization of demineralized dentin lesions adjacent to glass-ionomer cements (GICs) has been reported in the literature. This study tested the hypothesis that a strontium-based GIC can remineralize completely demineralized dentin by nucleation of new apatite crystallites within an apatite-free dentin matrix. Human dentin specimens were acid-etched, bonded with Fuji IXGP, and immersed in a calcium-and-phosphate-containing 1.5X simulated body fluid (SBF) for 1-4 months. Polyacrylic acid and polyvinylphosphonic acid biomimetic analogs were added to the SBFs to create 2 additional remineralization media. Specimens were processed by transmission electron microscopy (TEM). No apatite deposition could be identified in the completely demineralized dentin in any of the specimens immersed in the 3 remineralization media, despite TEM/EDX evidence of diffusion of ions specific to the strontium-based GIC into the demineralized dentin. The hypothesis was rejected; mineral concentration alone is not a sufficient endpoint for assessing the success of contemporary remineralization strategies. PMID:20110510

Apatite-binding peptides discovered by phage display provide an alternative design method for creating functional biomaterials for bone and tooth tissue repair. A limitation of this approach is the absence of display peptide phosphorylation--a post-translational modification important to mineral-binding proteins. To refine the material specificity of a recently identified apatite-binding peptide, and to determine critical design parameters (net charge, charge distribution, amino acid sequence and composition) controlling peptide affinity for mineral, we investigated the effects of phosphorylation and sequence scrambling on peptide adsorption to four different apatites (bone-like mineral, and three types of apatite containing initially 0, 5.6 and 10.5% carbonate). Phosphorylation of the VTKHLNQISQSY peptide (VTK peptide) led to a 10-fold increase in peptide adsorption (compared to nonphosphorylated peptide) to bone-like mineral, and a 2-fold increase in adsorption to the carbonated apatite, but there was no effect of phosphorylation on peptide affinity to pure hydroxyapatite (without carbonate). Sequence scrambling of the nonphosphorylated VTK peptide enhanced its specificity for the bone-like mineral, but scrambled phosphorylated VTK peptide (pVTK) did not significantly alter mineral-binding suggesting that despite the importance of sequence order and/or charge distribution to mineral-binding, the enhanced binding after phosphorylation exceeds any further enhancement by altered sequence order. Osteoblast culture mineralization was dose-dependently inhibited by pVTK and to a significantly lesser extent by scrambled pVTK, while the nonphosphorylated and scrambled forms had no effect, indicating that inhibition of osteoblast mineralization is dependent on both peptide sequence and charge. Computational modeling of peptide-mineral interactions indicated a favorable change in binding energy upon phosphorylation that was unaffected by scrambling. In conclusion

Apatite-binding peptides discovered by phage display provide an alternative design method for creating functional biomaterials for bone and tooth tissue repair. A limitation of this approach is the absence of display peptide phosphorylation – a post-translational modification important to mineral-binding proteins. To refine the material specificity of a recently identified apatite-binding peptide, and to determine critical design parameters (net charge, charge distribution, amino acid sequence and composition) controlling peptide affinity for mineral, we investigated the effects of phosphorylation and sequence scrambling on peptide adsorption to four different apatites (bone-like mineral, and three types of apatite containing initially 0, 5.6 and 10.5% carbonate). Phosphorylation of peptide VTKHLNQISQSY (pVTK) led to a 10-fold increase in peptide adsorption (compared to nonphosphorylated peptide) to bone-like mineral, and a 2-fold increase in adsorption to the carbonated apatite, but there was no effect of phosphorylation on peptide affinity to pure hydroxyapatite (without carbonate). Sequence scrambling of the nonphosphorylated VTK peptide enhanced its specificity for the bone-like mineral, but scrambled pVTK peptide did not significantly alter mineral-binding suggesting that despite the importance of sequence order and/or charge distribution to mineral binding, the enhanced binding after phosphorylation exceeds any further enhancement by altered sequence order. Osteoblast culture mineralization was dose-dependently inhibited by pVTK and to a significantly lesser extent by scrambled pVTK, while the nonphosphorylated and scrambled forms had no effect, indicating that inhibition of osteoblast mineralization is dependent on both peptide sequence and charge. Computational modeling of peptide-mineral interactions indicated a favorable change in binding energy upon phosphorylation that was unaffected by scrambling. In conclusion, phosphorylation of serine residues

Measurements of clumped isotopes of carbonate-bearing minerals are a powerful tool for reconstructing past surface temperatures and thermal histories of shallow crustal rocks. Because the clumped-isotope thermometer is based on homogenous-phase equilibrium, a sample's clumped-isotope temperature is susceptible to resetting through, for example, intracrystalline diffusion and redistribution of C and O isotopes during (re)heating or slow cooling. Quantitative knowledge of the kinetics of this resetting have received increasing attention (1-3) and is critical for understanding the meaning of clumped-isotope temperatures of samples with complex burial histories. To better constrain these kinetics and complement previous work (1-3) we performed heating experiments (400-700°C) on optical calcites and carbonate-bearing apatites. As previously observed (2-3), calcites exhibit non-first-order kinetics. The data were fit using a model that incorporates both diffusion and isotope-exchange reactions (4). The kinetics derived with this model using the optical-calcite heating experiments of (2) and those measured here are indistinguishable. The model predicts that subtle changes (>10°C) in measured calcite clumped-isotope temperatures can occur at burial temperatures between 60-100°C on million-year timescales. Though small, such changes may have an impact on clumped-isotope-based reconstructions of past surface temperatures and thermal histories. The derived kinetics were compared to clumped-isotope measurements of cogenetic calcites and apatites from slowly cooled carbonatite intrusions. Apparent temperatures are 70-140°C for apatites and 120-190°C for calcites. Measured temperatures for calcites match modeled temperatures using reasonable geological cooling rates. Natural apatite samples yield lower apparent temperatures than predicted based on the model. We propose that this difference is the result of annealment of structural damage in apatites (e.g., generated by

In order to evaluate apatite as a potential solid nuclear waste form and a contaminant sequestration agent, the complimentary use of single crystal X-ray diffraction and X-ray absorption spectroscopy (XAS) is applied to the study of U, Th, and Sr doped apatite single crystals to investigate the site preference, oxidation state, and structural distortions created by these substituents. Single crystal X-ray diffraction provides average information regarding the site occupancy of U and Th in apatites. Extended X-ray absorption fine-structure (EXAFS) yields quantitative information of the local structure of these substituents, which includes near-neighbor distances, coordination numbers and variations in bond distances; while X-ray absorption near edge structure (XANES) is used to determine the oxidation states of U. Restricted by the typical small size (20-100 μm) and volume of our synthetic samples, Micro-XAS is required. Different from studies which take full advantage of the polarization of synchrotron radiation, our Micro- XAS study on single crystal apatites was hampered by the polarization effects. In order to extract precise information of valence state and structural variation from XAS, it is necessary to know the crystallographic orientation of the sample with respect to the polarization direction of the incident X-ray beam during data collection. To do this we have designed and built a portable goniometer that duplicates the geometry of our laboratory standard Bruker Apex diffractometer goniometer. Crystal orientation is determined by X-ray diffraction at our home institution. The portable goniometer is then set up on the experimental table at synchrotron facilities and the crystal can be set in any specific known orientation. The lattice orientation determined by X-ray diffraction is applied to XAS data analysis, specifically calculation of scattering amplitudes and phase shifts, to account for polarization effects of synchrotron radiation. The goniometer

Hydrothermal experiments were conducted on high-silica (73-75 wt% SiO2), fluid-saturated melts at 844-862°C and ca. 50 MPa using crushed glass of the Los Posos rhyolite. Water and salts including NaCl, KCl, Ca(OH)2, and CaHPO4 and HCl were added proportionally to the experiments to restrict the variability of the aluminosity of the melt. The Durango apatite, which contains 3.53 wt% F and 0.41% Cl, was added as "seeds"<5µm in diameter to stimulate apatite growth during the experiments. Samples were loaded into gold capsules and run in cold-seal pressure vessels for durations of 286-1008 hours. Temperature was cycled at ±20˚C to promote apatite crystallization. Electron microprobe analyses of run-product glasses and embedded apatite grains support calculation of a range of partition coefficients ( = wt% Cl in apatite/wt% Cl in melt) of 4.7 to 15.9. The mole fraction of Cl in experimental apatites, or XCl, ranges from 0.19 to 0.56, while XF ranges from 0.08 to 0.63. The computed values for XOH range from 0.24 to 0.38. We find that normalizing XCl to XOH of apatites dramatically improves the precision when using apatite compositions to model Cl contents of melts. We compare our Los Posos rhyolite experiments with published data on 50 MPa rhyodacite experiments and find that Cl partitioning is significantly different in each system. Given the importance of chlorine in fluid equilibria, ore transport, and magma evolution, applications of apatite as a proxy for Cl contents in melts are unbounded. It is found that in order to accurately use the volatile composition of natural and synthetic apatites to calculate the volatile composition of melts in felsic systems, several chemical factors, including wt% SiO2 and the aluminosity/alkalinity of melts, should be incorporated as parameters to enhance relevant modeling. This allows geochemists to place better constraints on processes associated with crystallizing Cl-bearing magmatic systems.

The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

Apatite fission track thermochronometry (AFTT) has proved an invaluable tool for determining the cooling histories of rocks in the shallow crust. Quantitative models for the time and temperature dependence of the fission track annealing process in apatite demostrate that the combination of fission track apparent age and track length distribution provides a continuous record of the thermal history of the samples from 120 to 60^oC, and possibly, to lower temperatures. However the sensitivity of the technique is poorly constrained below 70-80^oC because annealing rates are slow. The apatite (U-Th)/He system is sensitive to temperatures between 80 and 40^oC irrespective of apatite chemistry, and presents a way to test the ability of AFTT to determine thermal histories below 80^oC. Here we present a novel way of combining apatite fission track and (U-Th)/He data that narrows the number of possible thermal histories and provides better constraints on the landscape evolution of a particular region. We use as an example the southeastern Australia passive margin in NSW, an area where post break-up landscape evolution is poorly resolved despite an extensive fission track database. Fission track and (U-Th)/He ages have been measured on 16 apatite samples from two coast perpendicular traverses across the coastal plain, up the escarpment onto the plateau. The fission track data are modelled using AFTSolve and the individual thermal histories which fit the data are used as parameters for forward modelling the apatite He ages. Only the thermal histories that produce the measured He age, within uncertainty, are considered. For each sample, the choosen time-temperature paths show the same peculiar characteristics, narrowing considerably the number of possible cooling scenarios. This combination shows that the AFT/derived thermal histories for temperatures between 60 to 40^oC may be inconsistent with the (U-Th)/He ages, suggesting that the annealing process at this temperatures

Conodonts are micro-fossils chemically composed of apatite which occurred in the body of one animal. They are guide fossils to show formation ages of sedimentary sequences with the highest resolution [1] and good samples to verify the dating method. We developed the ion microprobe U-Pb dating of apatite [2] and applied the method to a Carboniferous conodont [3] by using a SHRIMP II installed at Department of Earth and Planetary Sciences, Hiroshima University. Recently we have developed the NanoSIMS U-Pb dating method and successfully measured the formation ages of monazite [4] and zircon [5] at Atmosphere and Ocean Research Institute, University of Tokyo. In this work we carried out the NanoSIMS U-Pb dating of biogenic apatite such as conodont. Since the spot size of NanoSIMS is smaller than SHRIMP II, it is easier to have multi-spots on the single fragment of biogenic apatite. Based on the isochron method of U-Pb system, we have calculated the formation ages. They are consistent with those in literature. In order to study the chemical evolution of ocean during the past 600 Million years, strontium isotopes (87Sr/86Sr) of fossil marine carbonate such as coral skeletons and foraminifera tests were measured and compiled [6]. However they are not robust when the age is older than 500Ma, partly due to post-depositional histories. Apatite is more stable and more resistant to the alteration than carbonate [7]. Recently we have developed the method of NanoSIMS strontium isotopic analysis of a fish otolith, which composed of aragonite [8]. In this work we carried out the strontium isotopic analysis of biogenic apatite. The advantage of the ion microprobe technique over the TIMS (thermal ionization mass spectrometer) and MC-ICP-MS (multi-collector inductively coupled argon plasma mass spectrometer) method is preservation of the important textural context and to provide an opportunity for other simultaneous analytical work with high spatial resolution. This is the case for

Concentrations of rare earth elements (REE) have been measured on a suite of apatite crystals from an internally zoned granitic pegmatite enriched in Li, B, Be, F, Nb, Ta, Sn and U with a Cameca IMS 3f ion microprobe using energy filtering. An apatite specimen from the Tin Mountain pegmatite, analyzed previously by isotope dilution, was used as a standard. The chondrite-normalized pattern determined with the ion microprobe closely matches the pattern determined by isotope dilution, with maxima at Sm and Dy, and minima at Nd and Er. Apatite samples from the Bob Ingersoll pegmatite show a large range of REE patterns and concentrations. In one case, apatite crystals within millimeters show differences in REE concentrations and pattern shapes, including a switch from positive to negative Eu anomalies. These effects may be coupled with non-ideal partitioning of REE in a heterogeneous mixture of melt, aqueous fluid and crystals. REE concentrations in apatite samples from the different pegmatite zones indicate a large variation in outer zones, high concentrations near the pegmatite core, and very low concentration in the core. Patterns are flat to slightly inclined (Ce/Yb: 1 to 5), and most samples have positive Eu anomalies. The magnitude of positive Eu anomalies decreases with inward position in the pegmatite, possibly indicating a progressive increase in {line integral}O{sub 2}, and a sharp increase may be indicated by systematic Ce depletion in apatite from the pegmatite core. REE-specific volatile complexes may contribute to variations, including unusual kinks, observed in REE patterns of apatite from mineral assemblages in upper parts of the pegmatite.

In order to better constrain the evolution and petrogenesis of pegmatite, geochemical analysis was conducted on a suite of apatite crystals from the Altay Koktokay No. 3 pegmatite, Xinjiang, China and from the granitic and amphibolitic wall rocks. Apatite samples derived from pegmatite zones show convex tetrad effects in their REE patterns, extremely negative Eu anomalies and non-chondritic Y/Ho ratios. In contrast, chondritic Y/Ho ratios and convex tetrad effects are observed in the muscovite granite suggesting that different processes caused non-chondritic Y/Ho ratios and lanthanide tetrad effects. Based on the occurrence of convex tetrad effects in the host rocks and their associated minerals, we propose that the tetrad effects are likely produced from immiscible fluoride and silicate melts. This is in contrast to previous explanations of the tetrad effect; i.e. surface weathering, fractional crystallization and/or fluid-rock interaction. Additionally, we put forward that extreme negative Eu and non-chondritic Y/Ho in apatite are likely caused by the large amount of hydrothermal fluid exsolved from the pegmatite melts. Evolution of melt composition was found to be the primary cause of inter and intra-crystal major and trace element variations in apatite. Mn entering into apatite via substitution of Ca is supported by the positive correlation between CaO and MnO. Different evolution trends in apatite composition imply different crystallization environments between wall rocks and pegmatite zones. Based on the geochemistry of apatite samples, it is likely that there is a genetic relationship between the source of muscovite granite and the source of the pegmatite.

Apatite-type oxides ([A(I)4][A(II)6][(BO4)6]O2), particularly those of the rare-earth silicate and germanate systems, are among the more promising materials being considered as alternative solid oxide fuel cell electrolytes. Nonstoichiometric lanthanum silicate and germanate apatites display pure ionic conductivities exceeding those of yttria-stabilized zirconia at moderate temperatures (500-700 °C). In this study, mixed Si/Ge-based apatites were prepared by hydrothermal synthesis under mild conditions rather than the conventional solid-state method at high temperatures. Single-phase and highly crystalline nanosized apatite powders were obtained with the morphology changing across the series from spheres for the Si-based end member to hexagonal rods for the Ge-based end member. Powder X-ray and neutron analysis found all of these apatites to be hexagonal (P63/m). Quantitative X-ray microanalysis established the partial (<15 at%) substitution of La(3+) by Na(+) (introduced from the NaOH hydrothermal reagent), which showed a slight preference to enter the A(I) 4f framework position over the A(II) 6h tunnel site. Moreover, retention of hydroxide (OH(-)) was confirmed by IR spectroscopy and thermogravimetric analysis, and these apatites are best described as oxyhydroxyapatites. To prepare dense pellets for conductivity measurements, both conventional heat treatment and spark plasma sintering methods were compared, with the peculiar features of hydrothermally synthesized apatites and the influence of sodium on the ionic conductivity considered. PMID:24787953

Highlights: ► We use a Na{sub 2}SiO{sub 3} waste solution as source of Si. ► We present a simple, rapid and low temperature method of lanthanum silicate apatite preparation. ► TEOS, a high cost reagent, was successfully substituted by a cheap price Na{sub 2}SiO{sub 3}, to obtain pure La{sub 9.56}(SiO{sub 4})6O{sub 2.33} lanthanum silicate apatite. - Abstract: In recent years, apatite-type lanthanum silicates ([Ln{sub 10−x}(XO{sub 4})6O{sub 3–1.5x}] (X = Si or Ge)) have been studied for use in SOFC (solid oxide fuel cells), at low temperature (600–800 °C), due to its ionic conductivity which is higher than that of YSZ (Yttrium Stabilized Zirconia) electrolyte. For this reason they are very promising materials as solid electrolyte for SOFCs. Synthesis of functional nanoparticles is a challenge in the nanotechnology. In this work, apatite-type lanthanum silicate nanoparticles were synthesized by a water-based sol–gel process, i.e., sol–gel technique followed by chemical precipitation of lanthanum hydroxide on the gel of the silica. Na{sub 2}SiO{sub 3} waste solution was used as silica source. Spherical aerogel silica was prepared by acid catalyzed reaction, followed by precipitation of lanthanum hydroxide to obtain the precursor of apatite-type lanthanum silicate. Powders of apatite-type lanthanum silicate achieved from the precursor were characterized by thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area measurements (BET). The apatite phase was formed at 900 °C.

Apatite is a common igneous accessory mineral with a high saturation temperature which can therefore crystallize over a significant portion of magmatic compositional space. Sulfur presents an opportunity to identify zoning in apatites. Unlike other trace elements, sulfur is relatively immobile in the apatite crystal structure and can be present in typical concentrations up to 1500 - 2000 ppm (or 0.5 to 1 wt% SO3). Sulfur concentration zoning in igneous apatites from ore producing magmatic systems has been identified (Streck and Dilles, 1998), but the interpretation of the cause of this zoning remains an open question. δ34S isotopic ratios of whole apatites have been used to track isotopic evolution associated with changes in magma fO2 and eruptive degassing (Rye, 2005). The presented work combines sulfur concentration mapping in zoned apatite crystals with in-situ SIMS 34S and 32S isotope measurements. Apatites were extracted from granite to granodiorite samples from the Cadiz Valley Batholith in the central Mojave Desert. This batholith is related to the pulse of Cretaceous Cordilleran magmatism that generated large batholiths in the Sierra Nevada and the Penninsular Ranges. The Mojave segment of the Cretaceous arc is unique in their construction into a full thickness of continental crust which exerted a strong influence on magmatic compositions. Apatite grains were mounted parallel to C axes, ground until grains were approximately bisected, and analyzed by Electron Microprobe at UCLA, for CaO, P2O5, SO3 and SiO2. Grains were surveyed and those yielding anomalous SO3 contents were investigated by micron-scale concentration mapping. Typical SO3 concentrations of apatites from all samples were ~0.2 wt%, while 8 to 10% of apatite grains from two samples contained cores with concentrations ranging up to 0.5 wt%. The sulfur zoning in these samples is oscillatory, in some grains representing 5 to 6 repetitions of high and low concentrations. Based on these textures

Apatite fission-track ages of 168-83 Ma for 39 samples of Proterozoic crystalline rocks, three samples of Cambrian Potsdam sandstone, and one Cretaceous lamprophyre dike from the Adirondack Mountains in New York State indicate that unroofing in this region occurred from Late Jurassic through Early Cretaceous. Samples from the High Peaks section of the Adirondack massif yielded the oldest apatite fission-track ages (168-135 Ma), indicating that it was exhumed first. Unroofing along the northern, northwestern, and southwestern margins of the Adirondacks began slightly later, as shown by younger apatite fission-track ages (146-114 Ma) determined for these rocks. This delay in exhumation may have resulted from burial of the peripheral regions by sediment shed from the High Peaks. Apatite fission-track ages for samples from the southeastern Adirondacks are distinctly younger (112-83 Ma) than those determined for the rest of the Adirondack region. These younger apatite fission-track ages are from a section of the Adirondacks dissected by shear zones and post-Ordovician north-northeast-trending normal faults. Differential unroofing may have been accommodated by reactivation of the faults in a reverse sense of motion with maximum compressive stress, sigma1, oriented west-northwest. A change in the orientation of the post-Early Cretaceous paleostress field is supported by a change in the trend of Cretaceous lamprophyre dikes from east-west to west-northwest. PMID:10736267

Iron oxide-apatite deposits are present in Upper Eocene pyroxene-quartz monzonitic rocks of the Zanjan district, northwestern Iran. Mineralization occurred in five stages: (1) deposition of disseminated magnetite and apatite in the host rock; (2) mineralization of massive and banded magnetite ores in veins and stockwork associated with minor brecciation and calcic alteration of host rocks; (3) deposition of sulfide ores together with potassic alteration; (4) formation of quartz and carbonate veins and sericite, chlorite, epidote, silica, carbonate, and tourmaline alteration; and (5) supergene alteration and weathering. U-Pb dating of monazite inclusions in the apatite indicates an age of 39.99 ± 0.24 Ma, which is nearly coeval with the time of emplacement of the host quartz monzonite, supporting the genetic connection. Fluid inclusions in the apatite have homogenization temperatures of about 300 °C and oxygen isotopic compositions of the magnetite support precipitation from magmatic fluids. Late-stage quartz resulted from the introduction of a cooler, less saline, and isotopically depleted fluid. The iron oxide-apatite deposits in the Tarom area of the Zanjan district are typical of a magmatic-hydrothermal origin and are similar to the Kiruna-type deposits with respect to mineral assemblages, fabric and structure of the iron ores, occurrence of the ore bodies, and wall rock alteration.

The very existence of Grand Canyon inspires questions about why canyons are carved, how drainage systems and landscapes evolve, and how these processes relate to the elevation gain of plateaus. Yet when and why Grand Canyon was carved have been extraordinarily controversial for more than 150 years. Over the last several decades, the dominant view for the origin of the canyon is one of rapid incision at 5-6 Ma, when detritus derived from the upstream reaches of the Colorado River system appeared in Grand Wash Trough at the Colorado River's western exit from the Colorado Plateau. The absence of such diagnostic deposits prior to 6 Ma has been used to argue that Grand Canyon was not yet excavated (e.g., Karlstrom et al., 2008). However, a variety of data hint at a more ancient age for part or all of the canyon, and it has been proposed that a smaller drainage basin in largely carbonate lithologies could explain the absence of pre-6 Ma Colorado River clastics in Grand Wash Trough even if a significant Grand Canyon were present. Most recently, apatite (U-Th)/He (AHe) thermochronometry data from western Grand Canyon were used to infer excavation of this area to within several hundred meters of its modern depth by ca. 70 Ma (Wernicke, 2011), an interpretation in direct conflict with the young canyon model. The unexpected implications of the initial Grand Canyon AHe work motivated the apatite 4He/3He and U-Th zonation study presented here. Apatite 4He/3He thermochronometry provides information about the spatial distribution of radiogenic 4He in an apatite crystal that can better constrain a sample's cooling history. A key premise of AHe and 4He/3He spectra interpretation is that the He kinetic model used is accurate. We first investigate whether differing 4He/3He spectra for apatites of variable AHe date, radiation damage, and U-Th zonation from eastern Grand Canyon yield mutually consistent thermal history results using the RDAAM kinetic model, which must be true if the

Samples were collected in west to east transects across the Appalachian Basin of Pennsylvania, Maryland, West Virginia, and Virginia. These samples locations were chosen to test the concept of increasing paleotemperature due to increasing burial from west to east across the Appalachian Basin and to detect any thermal anomalies that exist. Calculated time-temperature (tT) paths based on apatite fission-track apparent ages and confined track length distributions for samples from this study indicate that both the Pennsylvania and southern Appalachian had complex uplift and cooling histories. In Pennsylvania, the Tioga and Kalkberg ash bed samples from central Pennsylvania yield modelled tT paths that indicate early post-Alleghanian (285-270 Ma) cooling with uplift estimated at beginning at {approx}251 {plus minus} 25 Ma. Samples from the western Allegheny Plateau and Allegheny Front contain apatites which have reset to give fission-track ages and track lengths consistent with tT histories beginning at <200 Ma. In northeastern Pennsylvania on the Allegheny Plateau, the modelled tT paths show rapid cooling from temperatures in the range of 110{degree}-120{degree} C at 170-160 Ma. In the southern Appalachian Basin, calculated tT paths indicate that uplift in the northern section was immediately post-Alleghanian folding with uplift beginning first in the northwestern section on the Cumberland Plateau at {approx}226 {plus minus} 23 Ma and progressing to the eastern Valley and Ridge Province of Virginia at {approx}119 {plus minus} 12 Ma. The samples from southwestern Virginia yield a mean apatite fission-track apparent age of 175 {plus minus} 11 Ma which may be the result of a higher heat flow, higher paleogeothermal gradient during the Upper Jurassic-Early Cretaceous extension along the Atlantic Coast.

Fungi play important roles in biogeochemical processes such as organic matter decomposition, bioweathering of minerals and rocks, and metal transformations and therefore influence elemental cycles for essential and potentially toxic elements, e.g., P, S, Pb, and As. Arsenic is a potentially toxic metalloid for most organisms and naturally occurs in trace quantities in soil, rocks, water, air, and living organisms. Among more than 300 arsenic minerals occurring in nature, mimetite [Pb5(AsO4)3Cl] is the most stable lead arsenate and holds considerable promise in metal stabilization for in situ and ex situ sequestration and remediation through precipitation, as do other insoluble lead apatites, such as pyromorphite [Pb5(PO4)3Cl] and vanadinite [Pb5(VO4)3Cl]. Despite the insolubility of mimetite, the organic acid-producing soil fungus Aspergillus niger was able to solubilize mimetite with simultaneous precipitation of lead oxalate as a new mycogenic biomineral. Since fungal biotransformation of both pyromorphite and vanadinite has been previously documented, a new biogeochemical model for the biogenic transformation of lead apatites (mimetite, pyromorphite, and vanadinite) by fungi is hypothesized in this study by application of geochemical modeling together with experimental data. The models closely agreed with experimental data and provided accurate simulation of As and Pb complexation and biomineral formation dependent on, e.g., pH, cation-anion composition, and concentration. A general pattern for fungal biotransformation of lead apatite minerals is proposed, proving new understanding of ecological implications of the biogeochemical cycling of component elements as well as industrial applications in metal stabilization, bioremediation, and biorecovery. PMID:25979898

Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr-based drugs are not totally elucidated. The local environment of Sr(2+) cations in biological apatites present in pathological and physiological calcifications in patients without such Sr-based drugs has been assessed. In this investigation, X-ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initio FEFF9 X-ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr(2+) cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr(2+) versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr(2+) cations will be localized into the apatite network. PMID:24365928

Significant interest has been in examining calcium phosphate ceramics, specifically β-tricalcium phosphate (β-TCP) (Ca3 (PO4)2 ) and synthetic hydroxyapatite (HA) (Ca10 (PO4)6 (OH)2 ), in composites and more recently, in fibrous composites formed using the electrospinning technique for bone tissue engineering applications. Calcium phosphate ceramics are sought because they can be bone bioactive, which means an apatite forms on their surface that facilitates bonding to bone tissue, and are osteoconductive. However, studies examining the bioactivity of electrospun composites containing calcium phosphates and their corresponding osteogenic activity have been limited. In this study, electrospun composites consisting of (20/80) HA/TCP nanoceramics and poly (ϵ-caprolactone) (PCL) were fabricated. Solvent and solvent combinations were evaluated to form scaffolds with a maximum concentration and dispersion of ceramic and pore sizes large enough for cell infiltration and tissue growth. PCL was dissolved in either methylene chloride (Composite-MC) or a combination of methylene chloride (80%) and dimethylformamide (20%; Composite-MC + DMF). Composites were evaluated in vitro for degradation, apatite formation, and osteogenic differentiation of human mesenchymal stem cells (MSCs) with an emphasis on temporal gene expression of osteogenic markers and the pluripotent gene Sox-2. Apatite formation and the osteogenic differentiation was the greatest for Composite-MC as determined by gene expression, protein production and biochemical markers, even without the presence of osteoinductive factors in the media, in comparison to Composite-MC + DMF and unfilled PCL mats. Sox-2 levels also reduced over time. The results of this study demonstrate that the solvent or solvent combination used in preparing the electrospun composite mats plays a critical role in determining their bioactivity which may, in turn, affect cell behavior. PMID:24264603

Rare earth element (REE) distributions in biogenic apatite were determined in over 200 samples from Cambrian to the Recent. Nondestructive instrumental neutron activation analysis techniques were adapted for analysis of low-mass microfossil samples. Tests for chemical contamination, interspecies, interlaboratory and interexperiment variations show that there is no fractionation of REE, so that ratios of rare earths are consistent throughout the entire group of samples. The REE signature of biogenic apatite is acquired after deposition but only at the sediment-water interface and is characteristic of the redox state of the environment of deposition. This original environmental signature is retained through subsequent burial and diagenesis. Cerium has been shown to be the rare earth element that is sensitive to oxidation-reduction variations in marine waters. This cerium variation is stated mathematically and called Ce/sub anom/. Comparison of Ce/sub anom/ in fish debris from different modern redox environments shows that values > -0.10 occur in fish debris deposited under reducing conditions, whereas Ce/sub anom/ values apatite of conodonts, fish debris and inarticulate brachiopods indicate that significant shifts in the overall redox balance of seawater occurred in ancient oceans. Cambrian through Silurian seas were dominated by anoxia, followed by a gradual change to oxidizing conditions in the Devonian. Oceans remained generally oxidizing throughout the Carboniferous and Lower Permian. In the Upper Permian and Lower Triassic anoxic conditions were again prevalent. This was followed by a return to an oxidizing oceanic environment in the Upper Triassic.

We present a new approach for modelling annealing of fission tracks in apatite, aiming to address various problems with existing models. We cast the model in a fully Bayesian context, which allows us explicitly to deal with data and parameter uncertainties and correlations, and also to deal with the predictive uncertainties. We focus on a well-known annealing algorithm [Laslett, G.M., Green, P.F., Duddy, I.R., Gleadow. A.J.W., 1987. Thermal annealing of fission tracks in apatite. 2. A quantitative-analysis. Chem. Geol., 65 (1), 1-13], and build a hierachical Bayesian model to incorporate both laboratory and geological timescale data as direct constraints. Relative to the original model calibration, we find a better (in terms of likelihood) model conditioned just on the reported laboratory data. We then include the uncertainty on the temperatures recorded during the laboratory annealing experiments. We again find a better model, but the predictive uncertainty when extrapolated to geological timescales is increased due to the uncertainty on the laboratory temperatures. Finally, we explictly include a data set [Vrolijk, P., Donelick, R.A., Quenq, J., Cloos. M., 1992. Testing models of fission track annealing in apatite in a simple thermal setting: site 800, leg 129. In: Larson, R., Lancelet, Y. (Eds.), Proceedings of the Ocean Drilling Program, Scientific Results, vol. 129, pp. 169-176] which provides low-temperature geological timescale constraints for the model calibration. When combined with the laboratory data, we find a model which satisfies both the low-temperature and high-temperature geological timescale benchmarks, although the fit to the original laboratory data is degraded. However, when extrapolated to geological timescales, this combined model significantly reduces the well-known rapid recent cooling artifact found in many published thermal models for geological samples.

Elasmobranchs (e.g. sharks and rays), like all fishes, grow continuously throughout life. Unlike other vertebrates, their skeletons are primarily cartilaginous, comprising a hyaline cartilage-like core, stiffened by a thin outer array of mineralized, abutting and interconnected tiles called tesserae. Tesserae bear active mineralization fronts at all margins and the tesseral layer is thin enough to section without decalcifying, making this a tractable but largely unexamined system for investigating controlled apatite mineralization, while also offering a potential analog for endochondral ossification. The chemical mechanism for tesserae mineralization has not been described, but has been previously attributed to spherical precursors, and alkaline phosphatase (ALP) activity. Here, we use a variety of techniques to elucidate the involvement of phosphorus-containing precursors in the formation of tesserae at their mineralization fronts. Using Raman spectroscopy, fluorescence microscopy and histological methods, we demonstrate that ALP activity is located with inorganic phosphate polymers (polyP) at the tessera-uncalcified cartilage interface, suggesting a potential mechanism for regulated mineralization: inorganic phosphate (Pi) can be cleaved from polyP by ALP, thus making Pi locally available for apatite biomineralization. The application of exogenous ALP to tissue cross-sections resulted in the disappearance of polyP and the appearance of Pi in uncalcified cartilage adjacent to mineralization fronts. We propose that elasmobranch skeletal cells control apatite biomineralization by biochemically controlling polyP and ALP production, placement and activity. Previous identification of polyP and ALP shown previously in mammalian calcifying cartilage supports the hypothesis that this mechanism may be a general regulating feature in the mineralization of vertebrate skeletons. PMID:24948547

Evidence for precipitation of authigenic carbonate fluorapatite (CFA) in Long Island Sound and Mississippi Delta sediments suggests that formation of CFA is not restricted to environments of active coastal upwelling. The authors present porewater data suggestive of CFA formation in both these areas. Application of a sequential leaching procedure, designed specifically to separate authigenic carbonate fluorapatite from other phosphorus-containing phases, including detrital apatite of igneous or metamorphic origin, provides strong supporting evidence for authigenic apatite formation in these sediments. The size of the authigenic apatite reservoir increases with depth, indicating continued formation of CFA during early diagenesis. This depth increase is mirrored by a decrease in solid-phase organic P at both sites, suggesting that CFA is forming at the expense of organic P. Mass balance considerations, application of diagenetic models to intersitital water nutrient data, and the saturation state of the interstitial water are consistent with this interpretation. Diagenetic redistribution of phosphorus among the different solid-phase reservoirs is observed at both sites, and results in near perfect retention of P by these sediments over the depth intervals sampled. Formation of CFA in continental margins which do not conform to the classically defined regions of phosphorite formation renders CFA a quantitatively more important sink than has previously been recognized. Including this reservoir as a newly identified sink for reactive P in the ocean, the residence time of P in the modern ocean must be revised downward. The implication for ancient oceans of CFA formation in continental margin sediments other than phosphorites is that phosphorite formation may be less a representation of episodicity in removal of reactive P from the oceans than of localized concentration of CFA in phosphatic sediments by secondary physical processes. 90 refs., 5 figs., 2 tabs.

Oxygen isotopes are a key tool for quantifying temperature and salinity of ancient sea water. Initially, pristine skeletal carbonates (preferentially LMC) have been utilized to monitor variations in the oxygen isotopic composition of past oceans. A high preservation potential of the primordial isotopic signature may also be awarded to conodonts. These microfossils consist of fluor-apatite (francolite) with a dense microcrystalline structure and therefore are comparatively insensitive with regard to diagenetic overprinting. Because conodonts are frequent in Devonian rocks and widely used as index fossils, their application for oxygen isotope analysis is espe-cially promising for this specific geological time interval. Laser-based microsampling or high-temperature combustion techniques (TC/EA) allows us to analyse microsamples of conodont apatite (0.5 to 1 mg). The oxygen isotope measurements are performed on trisilverphosphate after dissolving conodont apatite (0.5 to 1 mg) in nitric acid and precipitating the phosphate group as Ag_3PO_4. Conodont samples from different locations in Germany (Rheinisches Schieferge-birge) and the Czech Republic (Prague Basin) as well as from the United States (Iowa) and Morocco (Anti-Atlas) have been analysed. δ18Oapatite values are presented for the Lochkovian, Middle and Late Devonian. δ18Oapatite values for the Lochkovian (Prague Basin) vary between 18.5 and 19.0 ppm (δ18Oapatite values given in V-SMOW). Assuming an oxygen isotopic composition for Devonian seawater of -1 ppm (ice-free world), the δ18Oapatite values translate into tem-peratures of 26^o to 28^oC for the tropical Lochkovian ocean. Eifelian to Givetian conodonts (Rheinisches Schiefergebirge, Prague Basin) show δ18Oapatite values from 18.5 to 20.4 ppm, corresponding to paleotemperatures of 20 to 28^o C. The Middle to Late Devonian transition is mainly documented by conodonts from Iowa with δ18Oapatite values of 18 to 20 ppm (21-30^o C). Conodont δ18Oapatite

The timing and mechanism of uplift of the Colorado Plateau by ~1.9 km since the Cretaceous is a major question in Cordilleran tectonics. Resolving when the Colorado Plateau was unroofed can provide some insight into this problem, because erosional denudation commonly is linked with uplift. New (U-Th)/He apatite data constrain post-Cretaceous denudational patterns in the Grand Canyon region of the southwestern Colorado Plateau. This area is underlain by resistant limestone of the Permian Kaibab Formation and preserves discontinuous remnants of fluvial sandstone of the Triassic Moenkopi Formation. Tertiary "rim gravels" unconformably overlie this surface near the plateau margin. Stratigraphic and apatite fission-track data suggest that the area was buried by several kilometers of Mesozoic and Cenozoic strata prior to plateau uplift and regional unroofing. (U-Th)/He dates for individual detrital apatites from fourteen Moenkopi sandstone samples across this area 1) are significantly younger than the depositional age of the unit, indicating partial to complete He loss following deposition, and 2) display dates that are younger with increasing distance from the plateau margin, reflecting an overall pattern of southwest to northeast stripping of the overlying sedimentary package. Individual apatites from five Tertiary rim gravel samples did not undergo significant He loss following deposition, such that the distributions of dates reflect the denudation of source regions and impose a maximum timing constraint on gravel deposition following unroofing to the modern plateau surface. Our results suggest that the current plateau margin was buried by > 1.5 km of Cretaceous sediments prior to pulses of denudation in the Laramide and mid-Tertiary (40-35 Ma) that may be linked with uplift episodes at these times. Each denudational pulse was followed by rim gravel aggradation. Significant late-Tertiary unroofing and scarp retreat is most simply explained by integration of the

Nanocrystalline bredigite (Ca{sub 7}MgSi{sub 4}O{sub 16}) powders were synthesized by a simple solution combustion method. Phase pure bredigite powders with particle sizes ranging from 234 to 463 nm could be obtained at a relatively low temperature of 650 deg. C. The apatite-forming ability of the bredigite powders was examined by soaking them in a stimulated body fluid. The compositional and morphological changes of the powders before and after soaking were analyzed by X-ray diffraction and scanning electron microscopy and the results showed that hydroxyapatite was formed after soaking for 4 days.

In-situ, laser ablation U-Th-Sm/He dating is an emerging technique in thermochronology that has been proven as a means to date zircon and monzonite1-5. In-situ U-Th-Sm/He thermochronology eliminates many of the problems and inconveniences associated with traditional, whole grain methods, including; reducing bias in grain selection based on size, shape and clarity; allowing for the use of broken grains and grains with inclusions; avoiding bad neighbour effects; and eliminating safety hazards associated with dissolution. In-situ apatite laser ablation is challenging due to low concentrations of U and Th and thus a low abundance of radiogenic He. For apatite laser ablation to be effective the ultra-high-vacuum (UHV) line must have very low and consistent background levels of He. To reduce He background, samples are mounted in a UHV stable medium. Our mounting process uses a MicroHePP (Microscope Mounted Heated Platen Press) to press samples into FEP (fluorinated ethylene propylene) bonded to an aluminum backing plate. Samples are ablated using a Resonetics 193 nm excimer laser and liberated He is measured using a quadrupole mass spectrometer on the ASI Alphachron noble gas line; collectively this system is known as the Resochron. The ablated sites are imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol, a custom MatLab algorithm developed to enable precise and unbiased measurement of the ablated pit geometry. We use the well-characterized Durango apatite to demonstrate the accuracy and precision of the method. He liberated from forty-two pits, having volumes between 1700 and 9000 um3, were measured using the Resochron. The ablated sites were imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol. U, Th and Sm concentrations were measured by laser ablation and the U-Th-Sm/He age calculated by standard age equation. An age of 33.8±0.31 Ma was determined and compares well with conventional

The features of extraction of rare earth elements (REE) were considered from hydrate-phosphate precipitates of REE of apatite processing by nitric acid technology. The preliminary purification of nitrate solution of REE from impurities of titanium, aluminum, iron, uranium and thorium was suggested to obtain stable solutions not forming precipitates. Washing the extract was recommended with the evaporated reextract that allows to obtain directly on the cascade of REE extraction the concentrated solutions suitable for the separation into groups by the extraction method. Technical decisions were suggested for the separation of REE in groups without the use of salting-out agent.

The Gibbs free energy of hydroxyellestadite [Ca10(SiO4)3(SO4)3(OH)2] was estimated using mineral equilibria applied to analyzed assemblages from the experimental charges of Luhr (1990). The apatite analyses of Peng et al. (1997) were used in conjunction with new analyses of the oxides and silicates in this study. An ideal mixing model was employed for apatite combined with mixing models from MELTS (Ghiorso & Sack, 1994) and Gibbs free energy data from Robie & Hemingway (1995) for the other crystalline phases. The resultant equation of the Gibbs free energy vs. T for hydroxyellestadite is as follows: DG°T(elem) = [2.817(T - 273) - 11831]/1000 kJ/mol, T in K. The calculated entropy for hydroxyellestadite is 1944 J/mol.K at 1073 K and 2151 J/mol.K at 1227 K. Independent estimates of the entropy of hydroxyellestadite obtained with the method of Robinson & Haas (1983) are within 5% of these values. The thermodynamic data on hydroxyellestadite were used to calculate the locus of the reactions: 2Ca10(SiO4)3(SO4)3(OH)2 + 7S2 + 21O2 = 20CaSO4 + 6SiO2 + 2H2O 6Ca10(SiO4)3(SO4)3(OH)2 + 102SiO2 + 20Fe3O4 = 60CaFeSi2O6 + 6H2O + 9S2 + 37O2 2Ca10(SiO4)3(SO4)3(OH)2 + 10Mg2Si2O6 + 14SiO2 = 20CaMgSi2O6 + 2H2O + 3S2 + 9O2 in fO2-fS2 space at fixed P-T. Application of these equilibria to apatite zoned in sulfate from oxidized granitoids reflects a drop in fS2 by more than 1 log unit during its growth. The zoning is interpreted to represent the removal of a magmatic vapor phase during crystallization of these plutons. Removal of sulfur from magmas by hydrothermal fluids is important to the ore-forming process and to the production of acid sulfate aerosols during eruption of oxidized magmas. Preservation of sulfatian apatite may yield data on the sulfidation states of ancient flood basalts such as the Deccan Traps of India and the Parana basalts of Brazil to address the environmental impact of these giant eruptions.

Following growing interest in the use of ammonia as a fuel in solid oxide fuel cells (SOFCs), we have investigated the possible reaction between the apatite silicate/germanate electrolytes, La{sub 8+x}Sr{sub 2-x}(Si/Ge){sub 6}O{sub 26+x/2,} and NH{sub 3} gas. We examine how the composition of the apatite phase affects the reaction with ammonia. For the silicate series, the results showed a small degree of N incorporation at 600 deg. C, while at higher temperatures (800 deg. C), substantial N incorporation was observed. For the germanate series, partial decomposition was observed after heating in ammonia at 800 deg. C, while at the lower temperature (600 deg. C), significant N incorporation was observed. For both series, the N content in the resulting apatite oxynitride was shown to increase with increasing interstitial oxide ion content (x/2) in the starting oxide. The results suggest that the driving force for the nitridation process is to remove the interstitial anion content, such that for the silicates the total anion (O+N) content in the oxynitrides approximates to 26.0, the value for an anion stoichiometric apatite. For the germanates, lower total anion contents are observed in some cases, consistent with the ability of the germanates to accommodate anion vacancies. The removal of the mobile interstitial oxide ions on nitridation suggests problems with the use of apatite-type electrolytes in SOFCs utilising NH{sub 3} at elevated temperatures. - Graphical abstract: In this paper we show that heating the apatite-type electrolytes La{sub 8+x}Sr{sub 2-x}(Si/Ge){sub 6}O{sub 26+x/2} in NH{sub 3} at high temperatures leads to nitridation of the electrolyte, with the level of nitridation increasing with increasing x.

A combination of U-Pb LA-ICP-MS and ID-TIMS analyses of apatite has been used to investigate the high temperature (>450° C) thermal history of the Ecuadorian Andean margin. The rocks of the Eastern Cordillera of Ecuador evolved via terrane collision and accretion events, and active margin magmatism since the Early Jurassic. Low temperature (0.5) reveal periods of: i) rapid cooling (~240-220 Ma) through the Pb Partial Retention Zone (PRZ) shortly after crystallization, ii) residence at temperatures lower than the PRZ throughout the Jurassic, iii) reheating during 140-90 Ma, and iv) rapid cooling starting at 80-70 Ma. These findings corroborate conclusions based on geochronological and sedimentological data. Additional in-situ age transects and age-depth profiling of apatite are scheduled to determine the concentration distribution of radiogenic lead in the apatites, which will be used to constrain further the mechanisms of lead loss.

Secondary age standards are valuable in intra- and interlaboratory calibration. At present very few such standards are available for fission track dating that is older than Tertiary. Several altered volcanic ash beds occur in the Middle Jurassic Carmel Formation in southwestern Utah. The formation was deposited in a shallow marine/sabhka environment. Near Gunlock, Utah, eight ash beds have been identified. Sanidines from one of the ash beds (GUN-F) give a single-crystal laser-probe 40Ar/39Ar age of 166.3??0.8 Ma (2??). Apatite and zircon fission track ages range from 152-185 Ma with typically 15-20 Ma errors (2??). Track densities in zircons are high and most grains are not countable. Apatites are fairly common in most of the ash beds and have reasonable track densities ranging between 1.2-1.5 ?? 106 tracks/cm2. Track length distributions in apatites are unimodal, have standard deviations <1??m, and mean track lengths of about 14-14.5 ??m. High Cl apatites (F:Cl:OH ratio of 39:33:28) are particularly abundant and large in ash GUN-F, and are fairly easy to concentrate, but the concentrates contain some siderite, most of which can be removed by sieving. GUN-F shows evidence of some reworking and detriaal contamination based on older single grain 40Ar/39Ar analyses and some rounding of grains, but the apatite population appears to be largely uncontaminated. At present BJK has approximately 12 of apatite separate from GUN-F. ?? 1993.

A dense, uniform and highly biologically active bone-like apatite layer can be formed in arbitrary thickness on any kind and shape of solid substrate surface by the following biomimetic method at ordinary temperature and pressure. First, a substrate is set in contact with particles of bioactive CaO SiO2 based glass soaked in a simulated body fluid (SBF) with inorganic ion concentrations nearly equal to those of human blood plasma. Second, the substrate is soaked in another solution with ion concentrations 1.5 times those of SBF (1.5 SBF). In the present study, organic polymer substrates treated with 5 M NaOH solution were subjected to the above mentioned biomimetic process. The induction periods for the apatite nucleation on polyethyleneterephthalate (PET), polymethylmethacrylate (PMMA), polyamide 6 (PA6), and polyethersulfone (PESF) substrates were reduced from 24 to 12 h with the NaOH treatment. The adhesive strength of the formed apatite layer were increased from 3.5 to 8.6 MPa, from 1.1 to 3.4 MPa, and from 0.6 to 5.3 MPa with the NaOH treatment, for PET, PMMA, and PA 6, respectively. It was assumed that highly polar groups, such as carboxyl and sulfinyl ones formed by the hydrolysis of an ester group on PET and PMMA and of an amide group on PA 6, or of a sulfonyl group on PESF with the NaOH treatment, attached a large number of hydrated silica dissolved from the glass particles, to accelerate the apatite nucleation, and also to form a strong bond with the apatite. The apatite-organic polymer composites thus obtained are expected to be useful as bone-repairing as well as soft tissue-repairing materials. PMID:8580541

Apatite fission-track ages have been determined for 29 samples from two transects in the southern Appalachians. The northern transect extends from the VA Piedmont northwest through the Valley and Ridge Province, Cumberland Plateau, and into the Appalachian foreland of southeastern OH. An additional transect was collected from the Pine Mountain thrust in southeastern KY extending northwest to the Cincinnati Arch. Precambrian gneisses and granites from the VA Piedmont yield reset apatite fission-track ages ranging from 103 [+-] 6 to 138 [+-] 11 Ma. Ordovician through Mississippian sedimentary rocks from the Valley and Ridge Province of VA-WV also yield reset apatite fission-track ages ranging from 120 [+-] 8 to 144 [+-] 20 Ma. The cooling histories for the Piedmont and Valley and Ridge rocks of VA and WV thus appear similar, having cooled rapidly between about 103 and 144 Ma. Pennsylvanian samples from the Cumberland Plateau of WV yield rest apatite fission-track ages of 112 [+-] 7 to 169 [+-] 13 MA in the southeast which grade into partially reset (mixed ages) northwest of Charlestown (133 [+-] 13 to 156 [+-] 10 Ma). The Permian Dunkard Formation from the OH-WV border yielded a mixed age of 197 [+-] 13 Ma, suggesting that the Permian has not been subjected to temperatures > 100 C for times greater than 1 Ma, since it was deposited. Mississippian--Pennsylvanian samples from eastern KY yield reset apatite fission-track ages which decrease from the Pine Mt. Thrust (186 [+-] 16 Ma) to Mozelle, KY (136 [+-] 12 Ma), then increase toward the Cincinnati Arch (166 [+-] 18 [minus] 186 [+-] 21 Ma). This is consistent with older apatite fission-track ages (200 Ma) from Ordovician K-bentonites in the vicinity of the Cincinnati Arch.

Synthetic biopolymers are commonly used for the repair and regeneration of damaged tissues. Specifically targeting bone, the composite approach of utilizing inorganic components is considered promising in terms of improving mechanical and biological properties. We developed gelatin-apatite co-precipitates which mimic the native bone matrix composition within poly(lactide-co-caprolactone) (PLCL). Ionic reaction of calcium and phosphate with gelatin molecules enabled the co-precipitate formation of gelatin-apatite nanocrystals at varying ratios. The gelatin-apatite precipitates formed were carbonated apatite in nature, and were homogeneously distributed within the gelatin matrix. The incorporation of gelatin-apatite significantly improved the mechanical properties, including tensile strength, elastic modulus and elongation at break, and the improvement was more pronounced as the apatite content increased. Of note, the tensile strength increased to as high as 45 MPa (a four-fold increase vs. PLCL), the elastic modulus was increased up to 1500 MPa (a five-fold increase vs. PLCL), and the elongation rate was ~240% (twice vs. PLCL). These results support the strengthening role of the gelatin-apatite precipitates within PLCL. The gelatin-apatite addition considerably enhanced the water affinity and the acellular mineral-forming ability in vitro in simulated body fluid; moreover, it stimulated cell proliferation and osteogenic differentiation. Taken together, the GAp-PLCL nanocomposite composition is considered to have excellent mechanical and biological properties, which hold great potential for use as bone regenerative matrices. PMID:23985536

This report presents findings on biomimetic growth of hydroxyapatite (HAp) nanocrystals on Ti and sputtered TiO2 substrates. The possibility of TiO2 nanostructure as candidate materials for future biomedical applications has been explored through the comparison of microstructural and mechanical properties of bone like apatite grown on Ti and nano-TiO2 surfaces. Raman spectroscopy and x-ray diffraction studies reveal formation of carbonate apatite with apparent domain size in the nanoscale range. A better interaction at the nano-TiO2/nano-HAp interface due to higher interfacial area could promote the growth of bone like apatite. The crystal phases, crystallinity, and surface morphology of nano-TiO2 are considered as parameters to understand the nucleation and growth of apatite with different mechanical properties at the nanoscale. The methodology of x-ray line profile analysis encompasses deconvolution of merged peaks by preserving broadening due to nanosized HAp aggregates. The Young’s modulus of bone like apatite exhibits crystallographic directional dependence which suggests the presence of elastic anisotropy in bone like apatite. The lattice contraction in the c-direction is associated with the degree of carbonate substitution in the apatite lattice. The role of residual stress is critical for the lattice distortion of HAp deposited at physiological conditions of temperature and pH of human blood plasma. The ion concentration is crucial for the uniformity, crystallinity, and mechanical behaviour of the apatite.

In order to constrain the salinity of subduction zone fluids, piston-cylinder experiments have been conducted to investigate the partitioning behaviour of Cl and F in subducted sediments. These experiments were performed at H2O-undersaturated conditions with a synthetic pelite starting composition containing 800 ppm Cl, over a pressure and temperature range of 2.5-4.5 GPa and 630-900 °C. Repetitive experiments were conducted with 1900 ppm Cl + 1000 ppm F, and 2100 ppm Cl. Apatite represents the most Cl-abundant mineral phase, with Cl concentration varying in the range 0.1-2.82 wt%. Affinity for Cl decreases over the following sequence: aqueous fluid > apatite ⩾ melt > other hydrous minerals (phengite, biotite and amphibole). It was found that addition of F to the Cl-bearing starting composition significantly lowers the Cl partition coefficients between apatite and melt (DClAp-melt) and apatite and aqueous fluid (DClAp-aq). Cl-OH exchange coefficients between apatite and melt (KdCl-OHAp-melt) and apatite and aqueous fluid (KdCl-OHAp-aq) were subsequently calculated. KdCl-OHAp-melt was found to vary from 1 to 58, showing an increase with temperature and a decrease with pressure and displaying a regular decrease with increasing H2O content in melt. Mole fractions of Cl and OH in melt were calculated based on an ideal mixing model for H2O, OH, O, Cl and F. The Cl contents of other hydrous minerals (phengite, biotite and amphibole) fall between 200 and 800 ppm, with resultant Cl partition coefficients from 0.02 to 0.49, appearing independent of the bulk Cl and F content. Preliminary data from this study show that the partitioning behaviour of F is strongly in favour of apatite relative to melt and phengite, with DFAp-melt = 15-51. Apatites from representative eclogite facies metasediments were examined and found to have low Cl contents close to ∼100 ppm. Calculations using our experimentally determined KdCl-OHAp-aq of 0.004 at 2.5 GPa, 630 °C indicate a low

Determining the composition of apatites is important to understand the behavior of volatiles during planetary differentiation. Apatite is an ubiquitous magmatic mineral in the SNC meteorites. It is a significant reservoir of halogens in these meteorites and has been used to estimate the halogen budget of Mars. Apatites have been identified in sandstones and pebbles at Gale crater by ChemCam, a Laser-Induced Breakdown Spectroscometer (LIBS) instrument onboard the Curiosity rover. Their presence was inferred from correlations between calcium, fluorine (using the CaF molecular band centered near 603 nm, whose detection limit is much lower that atomic or ionic lines and, in some cases, phosphorus (whose detection limit is much larger). An initial quantification of fluorine, based on fluorite (CaF2)/basalt mixtures and obtained at the LANL laboratory, indicated that the excess of F/Ca (compared to the stoichiometry of pure fluorapatites) found on Mars in some cases could be explained by the presence of fluorite. Chlorine was not detected in these targets, at least above a detection limit of 0.6 wt% estimated from. Fluorapatite was later also detected by X-ray diffraction (with CheMin) at a level of approx.1wt% in the Windjana drill sample (Kimberley area), and several points analyzed by ChemCam in this area also revealed a correlation between Ca and F. The in situ detection of F-rich, Cl-poor apatites contrasts with the Cl-rich, F-poor compositions of apatites found in basaltic shergottites and in gabbroic clasts from the martian meteorite NWA 7034, which were also found to be more Cl-rich than apatites from basalts on Earth, the Moon, or Vesta. The in situ observations could call into question one of the few possible explanations brought forward to explain the SNC results, namely that Mars may be highly depleted in fluorine. The purpose of the present study is to refine the calibration of the F, Cl, OH and P signals measured by the ChemCam LIBS instrument, initiated

This paper reports on both cathodoluminescence (CL) and blue thermoluminescence (TL) emission of well-characterized natural Spanish and Brazilian apatites [Ca5(PO4)3(OH, F, Cl)]. Chemical analyses performed by means of Electron Microprobe Analysis (EMPA) have shown the presence of trace elements that can induce CL bands. In this sense, the apatites shown emission bands peaked at 3.26, 2.86, 2.62, 2.14, 2.02 and 1.94eV are respectively linked to substitutional Ce(3+), Tb(3+), Dy(3+), Pr(3+), Sm(3+) and Mn(2+) in structural Ca(2+) positions. The 3.18eV emission band can be associated with intrinsic electron defects on oxygen of the phosphate group (PO4)(3-). The presence of (UO2)(2+) gives rise to an emission at 2.14eV. All the studied aliquots exhibit one single UV-blue TL peak that modifies the position from one sample to another (370, 256 and 268°C) probably due to (i) the variation in the crystallinity index (from 0.88 to 1.34) and (ii) successive chemical processes such as oxidation, dehydration, dehydroxylation, and fluorine ions losses due to the thermal readout. PMID:24594886

Apatite fission track ages and confined-length distributions were collected from 38 basement outcrop and 5 basement drillcore samples in order to reconstruct the Phanerozoic thermal history of the Michigan Basin and southern Canadian Shield. The apatite data indicate two periods of thermal activity in the region: Triassic heating/cooling that affected the basin and adjacent shield and Cretaceous or post-Cretaceous heating/cooling that primarily affected the basin. The magnitude, timing, and cause of Cretaceous thermal activity cannot be identified with the present data. Model calculations suggest that some of the shield samples and probably all of the basin samples were heated to temperatures of at least 90C just prior to relatively rapid cooling in the Triassic. Available stratigraphic and geochemical constraints suggest that these elevated temperatures were the result of burial by an additional 2-5 km of late Paleozoic (probably Pennsylvanian and Permian) sediments. It is likely that the basin was buried during the Alleghenian Orogeny as observed for the adjacent Appalachian Basin.

Osteoconductive materials play a critical role in promoting integration with surrounding bone tissue and resultant bone repair in vivo. However, the impact of 3D osteoconductive substrates coupled with soluble signals on progenitor cell differentiation is not clear. In this study, we investigated the influence of bone morphogenetic protein-2 (BMP-2) concentration on the osteogenic differentiation of human mesenchymal stem cells (hMSCs) when seeded in carbonated apatite-coated polymer scaffolds. Mineralized scaffolds were more hydrophilic and adsorbed more BMP-2 compared to nonmineralized scaffolds. Changes in alkaline phosphatase (ALP) activity within stimulated hMSCs were dependent on the dose of BMP-2 and the scaffold composition. We detected more cell-secreted calcium on mineralized scaffolds at all time points, and higher BMP-2 concentrations resulted in increased ALP and calcium levels. RUNX2 and IBSP gene expression within hMSCs was affected by both substrate and soluble signals, SP7 by soluble factors, and SPARC by substrate-mediated cues. The present data indicate that a combination of apatite and BMP-2 do not simply enhance the osteogenic response of hMSCs, but act through multiple pathways that may be both substrate- and growth factor-mediated. Thus, multiple signaling strategies will likely be necessary to achieve optimal bone regeneration. PMID:21656707

Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix. PMID:27194462

Analysis of apatite from the Mine Block Intrusion (MBI) of the Lac des Iles Igneous Complex shows two pronounced trends in the halogens. Apatite from relatively fresh norite and melanorites from the Pd-sulfide zone contain up to 57 mol% chlorapatite endmember with significant hydroxyapatite component. In contrast, in altered rock (amphibolite and greenschist assemblages) the chlorapatite component is typically less than 10 mol% with wide variation in the F- and OH-endmember components. The latter trend is attributed to Cl loss to degassing and alteration, whereas the former is attributed to Cl enrichment in the ore-bearing rocks. It is suggested that the relatively H2O-rich and intermediate Cl content of the early igneous fluids degassed from the deeper levels of the MBI can explain the high Pd/Pt and Pd/Ir ratios of the deposit. A model is presented in which disseminated Pd-rich sulfides are initially introduced by a high-temperature magmatic fluid that also influenced crystallization to produce the gross modal variations of the igneous host rock. This high-temperature mineralization event was subsequently modified by the influx of late igneous and country fluids at amphibolite to greenschist conditions.

Analysis of apatite from the Mine Block Intrusion (MBI) of the Lac des Iles Igneous Complex show two pronounced trends in the halogens. Apatite from relatively fresh norite and melanorites from the Pd-sulfide zone contain up to 57 mole % chlorapatite endmember with significant hydroxyapatite component. In contrast, in altered rock (amphibolite and greenschist assemblages) and in the more evolved barren rocks the chlorapatite component is typically less than 10 mole % with wide variation in the F- and OH-endmember components. The latter trend is attributed to Cl loss to degassing and alteration whereas the former is attributed to Cl-enrichment in the ore-bearing rocks. It is suggested that the relatively H2O-rich and intermediate Cl content of the early igneous fluids degassed from the deeper levels of the MBI can explain the high Pd/Pt and Pd/Ir ratios of the deposit. A model is presented in which disseminated Pd-rich sulfide are initially introduced by a high temperature magmatic fluid that also influenced crystallization to produce the gross modal variations of the igneous host rock. This high temperature mineralization event was subsequently modified by the influx of late igneous and country fluids at amphibolite to greenschist conditions.

Alpine glaciers are efficient agents of erosion and capable of significantly modifying topography. Despite recent advances in theoretical and field studies that quantify glacial erosion processes, few studies have documented glacial erosion rates over long (>106 yr) or large (more than tens of kilometers) scales. We use apatite (U-Th)/He (AHe) and apatite fission track (AFT) cooling ages to address the late Miocene to Holocene erosion history across two 60-km-long transects of the heavily glaciated southern Coast Mountains, British Columbia. Observed AHe cooling ages from equal elevation samples range between 1.5 and 8 Ma and suggest that thick alpine glaciers resulted in a 16 km shift of the highest point in the topography in the past 1.5 4.0 m.y. We evaluated temporal and spatial variations in erosion rates using a three-dimensional thermal-kinematic model that predicted AHe and AFT ages at the surface for different erosion histories. Comparison of model predicted and observed cooling ages suggests an increase in erosion rates of as much as 300% over the past 1.5 7 m.y., coincident with the onset of glaciation of this range.

Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix. PMID:27194462

Rare earth silicate apatites are one-dimensional channel structures that show potential as electrolytes for solid oxide fuel cells (SOFC) due to their high ionic conductivity at intermediate temperatures (500-700 °C). This advantageous property can be attributed to the presence of both interstitial oxygen and cation vacancies, that create diffusion paths which computational studies suggest are less tortuous and have lower activation energies for migration than in stoichiometric compounds. In this work, neutron diffraction of Nd(28+x)/3AlxSi6-xO26 (0 ≤ x ≤ 1.5) single crystals identified the locations of oxygen interstitials, and allowed the deduction of a dual-path conduction mechanism that is a natural extension of the single-path sinusoidal channel trajectory arrived at through computation. This discovery provides the most thorough understanding of the O(2-) transport mechanism along the channels to date, clarifies the mode of interchannel motion, and presents a complete picture of O(2-) percolation through apatite. Previously reported crystallographic and conductivity measurements are re-examined in the light of these new findings. PMID:27015162

In this work we report a novel microwave assisted technology to deposit a uniform, ultra-thin apatite coating without any cracks on titanium implants in minutes. This method comprises of conventional biomimetic coating in synergism with microwave irradiation to result in alkaline earth phosphate nucleation. The microwave assisted coating process mainly follows the initial stages of biomimetic coating until the step of the Ca-P nuclei formation. After that, due to microwave irradiation more Ca-P nuclei are formed to cover the whole surface of the implant instead of the growth of deposited Ca-P nuclei to Ca-P globules and coatings. It is interesting to note the doping of Mg(2+) to Ca-P apatite coating can significantly change the properties and performances of as-deposited coatings. The hydrophilicity, physical properties, bioactivity, cell adhesion, and growth capability of as-deposited microwave assisted coatings were investigated. The study shows that this coating technology has great potential in biomedical applications. Additionally, since biomimetic coating can be applied to series of implant materials such as polymer, metals and glass, it is expected this microwave assisted coating technology can also be applied to these materials if they can remains stable at 100 °C, the boiling point of water. PMID:23910363

A novel strategy was employed to synthesize highly porous wollastonite-hydroxycarbonate apatite ceramic scaffolds for bone regeneration. A commercial liquid preceramic polymer filled with micro-CaCO3 powders was foamed at low temperature (at 350 °C), using the decomposition of a hydrazine additive, and then converted into ceramic by a treatment at 700 °C. Hydroxycarbonate apatite was later developed by a phosphatization treatment of ceramized foams, in a P-rich solution, while wollastonite was obtained by a second firing, at 900 °C. The effectiveness of the method was proven by x-ray diffraction analysis, showing the presence of the two expected crystalline phases. Porosity, interconnect size distribution and mechanical strength were in the range that is thought to be suitable for bone regeneration in non-load bearing sites (compressive strength ≈ 3 MPa, porosity ≈ 90%, modal interconnect diameter ≈ 130-160 μm). In addition, bioactivity and ion release rate were assessed in simulated body fluid (SBF). MC3T3 osteoblast precursor cells were able to colonize the material in vitro through the pore architecture and expressed osteogenic markers. PMID:27066770

Carbonate apatite (CO3Ap), the form of apatite found in bone, has recently attracted attention. The purpose of the present study was to histologically evaluate the tissue/cellular response toward the low-crystalline CO3Ap fabricated using a dissolution-precipitation reaction with set gypsum as a precursor. When set gypsum was immersed in a 100°C 1 mol/L Na3PO4 aqueous solution for 24 h, the set gypsum transformed into CO3Ap. Both CO3Ap and sintered hydroxyapatite (s-HAp), which was used as a control, were implanted into surgically created tibial bone defects of rats for histological evaluation. Two and 4 weeks after the implantation, histological sections were created and observed using light microscopy. The CO3Ap granules revealed both direct apposition of the bone matrix by osteoblasts and osteoclastic resorption. In contrast, the s-HAp granules maintained their contour even after 4 weeks following implantation which implied that there was a lack of replacement into the bone. The s-HAp granules were sometimes encapsulated with fibrous tissue, and macrophage polykaryon was occasionally observed directly apposed to the implanted granules. From the viewpoint of bone remodeling, the CO3Ap granules mimicked the bone matrix, suggesting that CO3Ap may be an appropriate bone substitute. PMID:26504813

The synthesis, characterization and the reactivity of apatitic calcium phosphates (Ca-HA, chemical formula Ca10(PO4)6(OH)2) is reported. Calcium carbonate (CaCO3) and potassium dihydrogen orthophosphate (KH2PO4) were selected as economical starting materials for the synthesis of Ca-HA under atmospheric conditions. Monocalcium phosphate monohydrate (MCPM), dicalcium phosphate dihydrate (DCPD), and octacalcium phosphate pentahydrate (OCP) were identified as the main intermediates of the synthesis reaction. The product obtained after 48 h of reaction contains mainly low-crystalline Ca-HA and small amounts of other calcium phosphates such as octacalcium phosphate (OCP), B-type carbonate apatite (CAP), as well as unreacted calcium carbonate. This Ca-HA was found to be active for the removal of Zn2+ from an aqueous solution. Its sorption capacity reached up to 120 mg of Zn2+ per g of Ca-HA powder after 24 h of reaction. The monitoring of soluble Zn, Ca and P during the sorption experiment allowed characterizing the mechanism of Zn uptake. Dissolution-precipitation, ionic exchange and surface complexation are the three main mechanisms involved in the sorption processes. The contribution of these mechanisms is discussed in detail.

Present paper is devoted to the research of the calcification processes in the blood plasma of human body. Spontaneous crystallization from the solution modeling the inorganic part of the blood plasma has been carried out. Obtained precipitates were studied by the various instrumental methods (X-ray powder diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, electron probe microanalysis and gas-volumetric method). All gathered data allow to summarize that nonstoichiometric carbonated hydroxyapatite with low crystallinity (CSD lengths 18-28 nm), high water content and small amount of chlorine ion was obtained throughout the syntheses. Part of vacancies at the Ca sites varies from 0.17 to 0.87; the value of the Cat/(P + C) ratio-from 1.52 to 1.64 (where Cat = Ca2+ + Na+ + K+ + Mg2+). The poor crystallized synthetic apatites with high carbonate ion content (from 4.34 to 5.54 wt%) and c parameter (6.888-6.894 Å) are analogues of the apatites of the pathological cardiovascular deposits. They can be obtained from the solution modeling human blood plasma by the inorganic components with calcium phosphate supersaturation 25 and 50 and with 10 and 12 weeks experiment time.

Mineralization is a ubiquitous process in the animal kingdom and is fundamental to human development and health. Dysfunctional or aberrant mineralization leads to a variety of medical problems, and so an understanding of these processes is essential to their mitigation. Osteoblasts create the nano-composite structure of bone by secreting a collagenous extracellular matrix (ECM) on which apatite crystals subsequently form. However, despite their requisite function in building bone and decades of observations describing intracellular calcium phosphate, the precise role osteoblasts play in mediating bone apatite formation remains largely unknown. To better understand the relationship between intracellular and extracellular mineralization, we combined a sample-preparation method that simultaneously preserved mineral, ions, and ECM with nano-analytical electron microscopy techniques to examine osteoblasts in an in vitro model of bone formation. We identified calcium phosphate both within osteoblast mitochondrial granules and intracellular vesicles that transported material to the ECM. Moreover, we observed calcium-containing vesicles conjoining mitochondria, which also contained calcium, suggesting a storage and transport mechanism. Our observations further highlight the important relationship between intracellular calcium phosphate in osteoblasts and their role in mineralizing the ECM. These observations may have important implications in deciphering both how normal bone forms and in understanding pathological mineralization. PMID:22879397

The investigation aims to demonstrate the conceptual thoughts behind developing mineral specific reagents for use in flotation of calcium containing ores. For this purpose, a series of dicarboxylate-based surfactants with varying distance between the carboxylate groups (one, two or three methylene groups) was synthesized. A surfactant with the same alkyl chain length but with only one carboxylate group was also synthesized and evaluated. The adsorption behavior of these new reagents on pure apatite and pure calcite surfaces was studied using Hallimond tube flotation, FTIR and ζ potential measurements. The relation between the adsorption behavior of a given surfactant at a specific mineral surface and its molecular structure over a range of concentrations and pH values, as well as the region of maximum recovery, was established. It was found that one of the reagents, with a specific distance between the carboxylate groups, was much more selective for a particular mineral surface than the other homologues. For example, out of the four compounds synthesized, only the one where the carboxylate groups were separated by a single methylene group floated apatite but not calcite, whereas calcite was efficiently floated with the monocarboxylic reagent, but not with the other reagents synthesized. This selective adsorption of a given surfactant to a particular mineral surface relative to other mineral surfaces as evidenced in the flotation studies was substantiated by ζ potential and infra-red spectroscopy data. PMID:25596367

Electrodeposition was used to prepare a new solid phase microextraction (SPME) coatings. Two apatite SPME coatings, dicalcium phosphate dihydrate (DCPD or brushite) and hydroxyapatite (HAP) were validly and homogeneously one-step electrodeposited on glassy carbon electrode (GCE) under different conditions. The coatings were characterized by XRD, FTIR, SEM, CV and EIS. The apatite SPME coatings showed excellent and selective adsorbability to fluoride ions. A novel indirect voltammetric strategy for sensitive detection of fluoride was proposed using K3Fe(CN)6 as indicating probe. The detection principle of fluoride ions was based on the increment of steric hindrance after fluoride adsorption, which resulting in the decrease of the amperometric signal to Fe(CN)6(3-). The liner ranges were 0.5-20.0 μmol/L for n-DCPD/GCE with the limit of detection of 0.14 μmol/L and 0.1-50.0 μmol/L for n-HAP/GCE with the limit of detection of 0.069 μmol/L, respectively. The developed method was applied to the analysis of water samples (lake, spring and tap water) and the recovery values were found to be in the range of 90-106%. PMID:24054624

The low modulus β-type Ti-45Nb alloy is a promising new implant alloy due to its excellent mechanical biocompatibility and composition of non-toxic elements. The effect of surface treatments on the evolution of controlled topography and roughness was investigated by means of scanning electron microscopy and optical profilometry. Severe mechanical treatments, for example sand-blasting, or etching treatments in strongly oxidizing acidic solutions, like HF:HNO(3) (4:1) or H(2)SO(4):H(2)O(2) (1:1) piranha solution were found to be very effective. In particular, the latter generates a nanopatterned surface topography which is expected to be promising for the stimulation of bone tissue growth. Compared to Ti and Ti-6Al-4V, the β-type Ti-45Nb alloy requires significantly longer etching durations due to the high chemical stability of Nb. Severe surface treatments alter the passive film properties, but do not deteriorate the outstanding corrosion resistance of the Ti-45Nb alloy in synthetic body fluid environments. The Ti-45Nb appears to have a lower apatite-formation ability compared to Ti. Etching with H(2)SO(4):H(2)O(2) (1:1) piranha solution inhibits apatite formation on Ti, but not on Ti-45Nb. PMID:23166048

The transition from osteoblast to osteocyte is described to occur through passive entrapment mechanism (self-buried, or embedded by neighboring cells). Here, we provide evidence of a new pathway where osteoblasts are "more" active than generally assumed. We demonstrate that osteoblasts possess the ability to migrate and differentiate into early osteocytes inside dense collagen matrices. This step involves MMP-13 simultaneously with IBSP and DMP1 expression. We also show that osteoblast migration is enhanced by the presence of apatite bone mineral. To reach this conclusion, we used an in vitro hybrid model based on both the structural characteristics of the osteoid tissue (including its density, texture and three-dimensional order), and the use of bone-like apatite. This finding highlights the mutual dynamic influence of osteoblast cell and bone extra cellular matrix. Such interactivity extends the role of physicochemical effects in bone morphogenesis complementing the widely studied molecular signals. This result represents a conceptual advancement in the fundamental understanding of bone formation. PMID:27150828

Aluminum (Al)-containing calcium-deficient carbonated hydroxyapatites were produced by a precipitation method from aqueous solution with carbonate (0-6.1%) and aluminum (0.1-0.5%) concentrations close to those found in biological materials. Two series of apatites were prepared: one at pH 7.0 and another at pH 9. 0. High-resolution electron microscopy has shown that many of them possess structural defects such as screw dislocations, grain boundaries, and central defects. Samples with high carbonate content and high water and high Al(3+) content had a high amount of structural defects. Accordingly, a sample (7Al1) with a relatively high carbonate content (6.1%) and a sample (7Al6) without carbonate but with a relatively high water (2.0 mol) and Al(3+) content (0. 39%) presented the highest amount of structural defects, 54% and 47%, respectively. A sample (7Al13) with a low level of crystalline water (1 mol) and low carbonate (2.5%) showed a small amount of defects. The presence of water associated with Al(3+) induced a high number of crystals having a central defect with a great similarity to the so-called water layer of octacalcium phosphate (OCP). Observed images of all these crystals have shown good correspondence with the computer-simulated image based on the crystal structure of hydroxyapatite, indicating that the addition of Al(3+) and carbonate does not perturb the apatitic structure. PMID:10679685

Past workers have used rare-earth element patterns recorded in biogenic apatite as proxies for original seawater chemistry. To explore the potency of this approach, we analyzed Pennsylvanian conodonts from limestones, gray shales, and black shales of the Fort Scott and Pawnee formations (Desmoinesian) and Swope and Dennis formations (Missourian) in Kansas, Missouri, and Iowa, U.S.A. Analysis of individual platform conodonts from seven taxa using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) revealed a consistent enrichment in the middle rare-earth elements (MREE). Analogous MREE enrichment has been observed in authigenic apatite and bulk samples of phosphate-rich black shales from the same formations. Importantly, however, phosphate-depleted shales intimately associated with the P-rich intervals are relatively depleted in MREE. These antithetic patterns argue convincingly for secondary migration from the bulk sediment into the phosphate, and the extent of MREE enrichment in the conodonts is correlated positively with the total REE content. MREE enrichment in conodonts does not vary systematically as a function of lithology, stratigraphic level, conodont genus, geographic location, or with independent estimates of paleoredox conditions in the bottom waters. Collectively, these results argue for postmortem (diagenetic) REE uptake resulting in a pronounced (and progressive) MREE enrichment. Any cerium anomalies, if initially present, were masked by diagenetic uptake of REE. Paleoenvironmental interpretations of conodont REE, particularly for samples exhibiting MREE enrichment, should therefore be viewed with caution.

The Cenozoic basanite from the Ostrzyca Proboszczowicka in Lower Silesia (SW Poland) belongs to numerous lavas occurring in the NE part of the Central European Volcanic Province. Basanite contains clinopyroxene megacrysts up to 3 cm in size. The clinopyroxene has the composition of aluminian-sodian diopside (mg# 0.61-0.70, 0.08-0.12 atoms Na pfu and 0.88-0.93 atoms Ca pfu). Cr is absent. The REE contents are above the primitive mantle reaching up to 18 x PM at Nd. Primitive-mantle normalized REE patterns show enrichment in LREE relative to HREE (LaN/LuN=3.81-5.01). The REE patterns of all the megacrysts show deflection in La-Nd. The trace element patterns are characterized by positive Zr, Hf and in some cases also Ta anomalies, and negative U, La, Sr, Ti and Pb ones. In some samples strong depletion (down to 0.01 x PM) in Rb and Ba is observed.The Ostrzyca megacrysts formed cumulate, which crystallized from magma similar to the host basanite, but more fractionated and enriched in REE, particularly in LREE (Lipa et al., 2014). This happened at mid-crustal depths (10-15 km) and the new pulse of basanitic magma entrained the crystals forming the non-solidified cumulate and brought them to the surface (Lipa et al., 2014). Clinopyroxene megacrysts contain large, transparent, euhedral apatite crystals up to 7 mm. The major element composition indicates the fluor-apatite with F content ranging from 0.87 to 1.93 wt.%. Chlorine content is strongly variable between grains (0.05-1.75 wt.%). Apatite is strongly enriched in LREE relative to HREE (LaN/LuN=60.39-62.23, about 1000 x PM for LREE and about 10 x PM for HREE). The REE patterns are nearly linear, with slight positive Nd and Gd anomalies. The trace element patterns are characterized by very strong negative anomalies of HFSE (Nb, Ta, Zr, Hf, Ti) and Pb, and weaker negative Sr anomaly. Concentration of Yb and Lu is on the level 10 x PM, whereas Rb, Hf and Ti are depleted relative to PM. Apatite preceded clinopyroxene

In the present study two nanocrystalline apatites have been investigated as bone-specific drug delivery devices to be used for treatment of bone tumors either by local implantation or by injection. In order to assess how the Ca/P ratio can influence the adsorption and release of anticancer platinum-bisphosphonate complexes, two kinds of apatite nanocrystals having different Ca/P ratios but similar morphologies, degree of crystallinity, and surface areas have been synthesized and characterized. The two platinum-bisphosphonate complexes considered were the bis-{ethylenediamineplatinum(ii)}-2-amino-1-hydroxyethane-1,1-diyl-bisphosphonate and the bis-{ethylenediamineplatinum(ii)}medronate. The Ca/P ratio plays an important role in the adsorption as well as in the release of the two drugs. In fact, the apatite with a higher Ca/P ratio showed greater affinity for both platinum complexes. Also the chemical structure of the two Pt complexes appreciably affects their affinity towards as well as their release from the two kinds of apatites. In particular, the platinum complex whose bisphosphonate contains a free aminic group showed greater upload and smaller release. The cytotoxicity of the Pt complexes released from the apatite was tested against human cervical, colon, and lung cancer cells as well as against osteosarcoma cells. In agreement with previous work, the Pt complexes released were found to be more cytotoxic than the unmodified complexes.In the present study two nanocrystalline apatites have been investigated as bone-specific drug delivery devices to be used for treatment of bone tumors either by local implantation or by injection. In order to assess how the Ca/P ratio can influence the adsorption and release of anticancer platinum-bisphosphonate complexes, two kinds of apatite nanocrystals having different Ca/P ratios but similar morphologies, degree of crystallinity, and surface areas have been synthesized and characterized. The two platinum

Igneous apatite crystals contain a record of the evolving concentrations of magmatic volatile elements such as F, H, and Cl during crystallization and degassing. In order to develop apatite as a quantitative barometer of magmatic volatile species, improved understanding of apatite-melt volatile equilibria is needed. We conducted apatite crystallization experiments using a piston cylinder apparatus at 1,200°C and 1 GPa. Apatite crystals were grown from an Fe- and Cl-free, haplobasaltic-andesite melt of constant composition. Experiments were quenched to below 700°C in 15 seconds, producing homogeneous glass plus apatite crystals ranging from 5 to 30 microns in diameter. Apatite and coexisting glass were analyzed using the Cameca ims 6f SIMS, with an O- beam and positive secondary ions, following the methods of Boyce and Hervig (2008, 2009), but using the inversion-based calibration routines of Boyce and Eiler (this meeting). These measurements provide the first direct constraint on the partitioning of hydrogen between apatite and melt. For the exchange reaction F-(melt) + OHapatite = OH-(melt) + Fapatite, the Keq was calculated from the measured data to be ~25, consistent with the results of Mathez and Webster (2004) and Webster et al. (2008), despite our experiments being nominally Cl- and Fe-free. Significant non-Henrian behavior is observed for hydrogen, but trace F behaves effectively Henrian at low concentrations, again consistent with previous work. These preliminary results reinforce the assertion that simple Henry's or Raoult's Law models of volatile partitioning between apatite and melt are rarely - if ever - appropriate, and that both F and H concentrations must be considered in order to use hydrogen concentrations in apatite to determine concentrations of hydrogen in the coexisting melt.

The oxygen isotope fractionation between the structural carbonate of inorganically precipitated hydroxyapatite (HAP) and water was determined in the range 10-37 °C. Values of 1000 ln α( CO32--HO) are linearly correlated with inverse temperature (K) according to the following equation: 1000 ln α( CO32--HO) = 25.19 (±0.53)· T-1 - 56.47 (±1.81) ( R2 = 0.998). This fractionation equation has a slightly steeper slope than those already established between calcite and water ( O'Neil et al., 1969; Kim and O'Neil, 1997) even though measured fractionations are of comparable amplitude in the temperature range of these experimental studies. It is consequently observed that the oxygen isotope fractionation between apatite carbonate and phosphate increases from about 7.5‰ up to 9.1‰ with decreasing temperature from 37 °C to 10 °C. A compilation of δ 18O values of both phosphate and carbonate from modern mammal teeth and bones confirms that both variables are linearly correlated, despite a significant scattering up to 3.5‰, with a slope close to 1 and an intercept corresponding to a 1000 ln α( CO32--PO43-) value of 8.1‰. This apparent fractionation factor is slightly higher or close to the fractionation factor expected to be in the range 7-8‰ at the body temperature of mammals.

Apatite fission-track (FT) and single grain (U-Th)/He ages from four vertical profiles in central Dronning Maud Land (East Antarctica) range from 312 ± 20 Ma to 135 ± 11 Ma and 304 ± 28 Ma to 104 ± 8 Ma, respectively. The combined age data allows to discriminate between undisturbed cooled (due to exhumation) and thermally overprinted crustal blocks. Profiles at the Zwieselhöhe and the Conradgebirge revealed unusual apatite FT vs. elevation relationships and (U-Th)/He ages older than the corresponding central apatite FT ages, possibly providing evidence for a Jurassic thermal overprint. Most probably Jurassic magmatism and associated advective heating led to total annealing of the apatite fission-tracks but helium only partially diffused. The model developed in this paper suggests that the (U-Th)/He ages from the Zwieselhöhe and Conradgebirge profiles are in part relicts of the pre-Jurassic cooling history. Two thermally undisturbed vertical profiles are used to record the long-term cooling history of central Dronning Maud Land. Time-temperature paths derived from modelled apatite FT data of these profiles revealed two phases of accelerated cooling during the Late Carboniferous and the Early Jurassic. Both phases are followed by slow cooling which is also documented by the spread in apatite (U-Th)/He single grain ages. The cooling at the end of the Carboniferous is most probably related to far field effects associated to the prevailing convergent tectonics. During the initial separation between East Antarctica and Mozambique erosion along an evolving rift shoulder caused the Jurassic cooling. Denudation of the basement was simultaneous with volcanism with both pre-dating (c. 20-10 Ma) sea-floor spreading in the Riser Larsen Sea (c. 155 Ma). Post Jurassic cooling was restricted to the lowest temperature sensitivity of both methods. Combined inverse modelled apatite FT data and forward modelled (U-Th)/He data suggest an Eocene/Oligocene cooling step, possibly

Hydrogen powered solid oxide fuel cells (SOFCs) are of enormous interest as devices for the efficient and clean production of electrical energy. However, a number of problems linked to hydrogen production, storage and transportation are slowing down the larger scale use of SOFCs. Identifying alternative fuel sources to act as intermediate during the transition to the full use of hydrogen is, therefore, of importance. One excellent alternative is ammonia, which is produced on a large scale, is relatively cheap and has the infrastructure for storage and transportation already in place. However, considering that SOFCs operate at temperatures higher than 500 {sup o}C, a potential problem is the interaction of gaseous ammonia with the materials in the cathode, anode and solid electrolyte. In this paper, we extend earlier work on high temperature reactions of apatite electrolytes with NH{sub 3} to the transition metal (Co) doped systems, La{sub 9.67}Si{sub 5}CoO{sub 26} and La{sub 10}(Si/Ge){sub 5}CoO{sub 26.5}. A combination of PXRD, TGA and XAFS spectroscopy data showed a better structural stability for the silicate systems. Apatite silicates and germanates not containing transition metals tend to substitute nitride anions for their interstitial oxide anions, when reacted with NH{sub 3} at high temperature and, consequentially, lower the interstitial oxide content. In La{sub 9.67}Si{sub 5}CoO{sub 26} and La{sub 10}(Si/Ge){sub 5}CoO{sub 26.5} reduction of Co occurs as a competing process, favouring lower levels of nitride-oxide substitution. -- Graphical Abstract: In reactions between the apatites La{sub 9.67}Si{sub 5}CoO{sub 26} and La{sub 10}(Si/Ge){sub 5}CoO{sub 26.5} and NH{sub 3} (g) at temperatures T>500 {sup o}C, the partial substitution of the Si and Ge by Co seems to discourage O{sup 2-}/N{sup 3-} substitution in favour of the reduction of the metal. Display Omitted

Intermediate to silicic volcanic eruptions often emit more S than predicted by petrological models -- this is called the "excess S problem." While most common minerals in these magmas are poor in volatile elements, the occurrence of large phenocrysts of S-rich haüyne (up to ~13 wt% SO3) in phonolites holds much promise for better constraining volcanic volatile budgets in differentiated alkaline magmatic systems. We have examined textural zonation patterns in haüyne separates from Tenerife (Spain), using mineral oil to enhance grain transparency. Included phases were characterized by energy dispersive spectroscopy, X-ray maps, and Raman spectroscopy. Slow growth of haüyne, inferred from zones with few inclusions, likely represents cooling-induced crystallization from S-rich melt during storage in the upper crust. By contrast, rapid growth of phenocrystic haüyne, generating "wispy" zones containing Fe-rich haüyne laths and zones rich in melt inclusions, fluid inclusions, and Fe-sulfide inclusions, may be associated with magma recharge and/or upward percolation of a low-density fluid phase (i.e., "gas sparging"). Both processes could bring new pulses of S from deep within the magmatic system. Zones containing thousands of fluid inclusions provide direct physical evidence that the melt was fluid-saturated during periods of rapid haüyne growth. Transfer of S-rich fluid should occur in all volatile-rich magmatic systems, including dacitic-rhyolitic arc systems with large S excesses, but is difficult to document in such magmas devoid of a large S-rich mineral phase like haüyne. Apatite, a mineral present in all volcanic rocks, may also contain information about S. We have observed intricate chemical zonation in backscattered electron images of apatite microphenocrysts from the same Tenerife samples. Variations in volatile and trace element concentrations between successive zones (measured via wavelength dispersive spectroscopy and laser ablation-inductively coupled

The only apatite-iron oxide ores in the classic Palaeoproterozoic Bergslagen ore province, central Sweden, occur semi-continuously between Grängesberg and Idkerberget. Together, they represent the largest concentration of iron ore in this part of the Fennoscandian shield. Their mineralogy, geochemistry, geometry and host rock relations all suggest that they belong to the Kiruna-type class of deposits. The apatite-iron oxide ores in Bergslagen are hosted by 1.9 Ga variably altered, metavolcanic to meta-subvolcanic rocks ranging from rhyolitic to andesitic in composition. The region has been affected by three episodes of deformation (D1-3) and regional, greenschist to amphibolite facies metamorphism during the c. 1.9-1.8 Ga Svecokarelian orogeny. The Grängesberg deposits occur as narrow, moderately SE-dipping lenses that are concordant to S0 surfaces in the host rocks. Magnetic anomaly data indicate that they extend to a depth of at least 1.7 km. The lens geometry is mainly controlled by deformation during D2. Reverse, oblique, top-to-the NNW shear is evident in the footwall, and strain partitioning due to competence contrasts between the ore and altered host rocks resulted in flattening at competent ore lens crests, leading to asymmetrical folds with opposite vergence towards pinch areas where prolate strain prevailed. D1 is evident as a crenulated cleavage and D3 appears as gentle, large-scale open folds. Geochemical data on host rocks show a systematic enrichment in REE from the least to the most altered rocks. The ore-associated alteration assemblages and the apatite-iron oxide ore feature similar and elevated REE concentrations and profiles, suggesting a link between hydrothermal alteration and oxide ore formation. However, most ore magnetite has δ18O values between +0.3 and +3.4 ‰ (ranging from -0.4 to +4.9 ‰), consistent with fractionation of oxygen between magnetite and a felsic to intermediate magma at high temperatures (Jonsson et al. 2011). These

Tissue engineering has become a new approach for repairing bony defects. Highly porous osteoconductive scaffolds perform the important role for the success of bone regeneration. By biomimetic strategy, apatite-coated porous biomaterial based on silk fibroin scaffolds (SS) might provide an enhanced osteogenic environment for bone-related outcomes. To assess the effects of apatite-coated silk fibroin (mSS) biomaterials for bone healing as a tissue engineered bony scaffold, we explored a tissue engineered bony graft using mSS seeded with osteogenically induced autologous bone marrow stromal cells (bMSCs) to repair inferior mandibular border defects in a canine model. The results were compared with those treated with bMSCs/SS constructs, mSS alone, SS alone, autologous mandibular grafts and untreated blank defects. According to radiographic and histological examination, new bone formation was observed from 4 weeks post-operation, and the defect site was completely repaired after 12 months for the bMSCs/mSS group. In the bMSCs/SS group, new bone formation was observed with more residual silk scaffold remaining at the center of the defect compared with the bMSCs/mSS group. The engineered bone with bMSCs/mSS achieved satisfactory bone mineral densities (BMD) at 12 months post-operation close to those of normal mandible (p>0.05). The quantities of newly formed bone area for the bMSCs/mSS group was higher than the bMSCs/SS group (p<0.01), but no significant differences were found when compared with the autograft group (p>0.05). In contrast, bony defects remained in the center with undegraded silk fibroin scaffold and fibrous connective tissue, and new bone only formed at the periphery in the groups treated with mSS or SS alone. The results suggested apatite-coated silk fibroin scaffolds combined with bMSCs could be successfully used to repair mandibular critical size border defects and the premineralization of these porous silk fibroin protein scaffolds provided an

Models for the nelsonite formation are currently highly contentious, with liquid immiscibility and fractional crystallization as frequently proposed formation mechanisms. The nelsonites in the Damiao massif anorthosite complex in the North China Craton and experimental evidence are revisited for the existence of silica-free CaO-FeO-Fe2O3-TiO2-P2O5 immiscible nelsonitic liquids. Our results of differential scanning calorimetry (DSC) demonstrate that nelsonite with the composition of one-third apatite and two-thirds Fe-Ti oxides by weight completely melts well above 1450 ºC, which is in good agreement with numerous experimental studies of the CaO-P2O5-FexO system in connection to metallurgy. Thus, the composition cannot be molten at temperatures relevant for crystallization of the Damiao magma. A review of experimental studies of liquid immiscibility and analyses of natural immiscible glasses show that all the liquids on the Fe- and P-rich side of the miscibility gap have at least 20 wt. % of aluminosilicate components. Main results of this study come from the analyses of apatite-hosted melt inclusions in Damiao nelsonite. The inclusions range from ~3 to 200 μm in diameter. They are ubiquitous and meet all the morphological criteria of primary melt inclusions crystallised into assemblages of daughter minerals. Almost all of them contain vermiculite and chlorite, and some contain biotite, amphibole, phlogopite and Fe-Ti oxides. Out of dozens analysed inclusions, only three have high contents of SiO2 (62.1-73.8 wt. %) and low contents of FeO (0.25-2.35 wt. %). Bulk compositions of other inclusions show large variations in SiO2 (20.79-50.16 wt. %) and FeOt (13.44-32.78 wt. %). With a few exceptions, the inclusions are very low in CaO (0.04-1.51 wt. %, and high in Al2O3 (10-21.17 wt. %). Despite the high Fe content, the compositions differ from those of the typical immiscible Fe-rich melts. It appears that the cumulus apatite crystallised from Fe-rich, hydrated

The thermal history of the Drummond Basin in central Queensland (Australia) has only been partly investigated. Inverse thermal modeling of apatite and zircon (U-Th)/He data can reveal the complex thermal history of sedimentary basins. We performed (U-Th)/He dating for detrital apatite and zircon grains extracted from five sandstone samples from the Campaspe DDH-1 drill hole. Mean apatite helium ages generally increase from 65.9 Ma (depth = 538 m) to 83.8 Ma (depth = 263 m). The deeper four samples yielded mean zircon helium (ZHe) ages of 289.7 - 278.2 Ma, with a systematic increase of the ZHe ages from deep to shallow samples. The shallowest sample (depth = 117 m) yielded a mean ZHe age of 263.6 Ma. Our inverse thermal modeling suggests five thermal events since burial: (1) rapid heating to the maximum temperature of 180~380 oC during ~320-290 Ma, (2) rapid cooling from ~260 oC to ~80 oC during ~290-240 Ma, (3) subdued cooling from ~80 oC to ~30 oC during ~240-200 Ma, (4) slow heating from ~30 oC to ~80 oC during ~200-80 Ma, followed by (5) rapid cooling from ~80 oC to ~35 oC at ~80 Ma. The timing and temperature conditions of the initial thermal event are consistent with K/Ar ages and temperatures deduced from illite. This period was characterized by voluminous regional magmatism and crustal extension preceding opening of the overlying Bowen Basin. Rapid cooling during ~290-240 Ma identified by our inverse thermal modeling roughly coincides with the thermal relaxation phase and foreland basin phase of the overlying Bowen Basin. This rapid cooling was probably a result of cessation of extension and subsequent contractional events to the east of Bowen Basin. Cooling slowed down during ~240-200 Ma. The Drummond Basin probably underwent serious erosion during this period, coeval with the peneplanation phase of the Bowen Basin. As is delineated by our modeling, the Drummond Basin was slowly heated from ~20 oC to ~90 oC during ~200-80 Ma, synchronous with development of

Bone-like apatite was precipitated on the surface of thermal sprayed calcium phosphate coatings following in vitro incubation in a simulated body fluid. The coatings were initially deposited on titanium alloy substrates by the high velocity oxy-fuel (HVOF) spray technique. Structural characterization and mechanical evaluation of the precipitated apatite layer were conducted. Results showed that the precipitation rate was directly influenced by the local Ca(2+) concentration in the vicinity of the coating's surface and that preferential dissolution of certain phases was found to accelerate the precipitation of the bone-like apatite. The dense precipitates exhibited a competitive Young's modulus value of approximately 120GPa, which was obtained through nanoindentation. This compared favorably to the calcium phosphate matrix. Differences in microstructure at various locations within the layer resulted in altered Young's modulus and microhardness values. Precipitation mechanism investigation was carried out through a comparative experiment. Chemical analysis showed that the precipitation of bone-like apatite on the calcium phosphate coating was quite conceivably a partial diffusion-controlled process. PMID:12485795

Recently Miles et al. (2014) proposed that a negative correlation between oxygen fugacity (expressed as logfO2 and the Mn content of apatite from a range of intermediate to silicic igneous rocks could be used as an oxybarometer (Eq. (1)).

Recent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile-bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk-rock basaltic composition and that of bulk-mesostasis regions, indicating that bulk-rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late-stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO2 abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite-melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.

Recent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile-bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk-rock basaltic composition and that of bulk-mesostasis regions, indicating that bulk-rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late-stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO2 abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite-melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.

Application of high temperature (>350oC) thermochronology is limited to the U-Pb system of accessory minerals, such as apatite, under the assumption that radiogenic lead is lost to thermally activated volume diffusion into an infinite reservoir. Cochrane et al. (2015) have demonstrated a working example from the northern Andes of South America. Predictions from volume diffusion theory were compared with measured single grain U-Pb date correlated to shortest diffusion radius and in-situ profiles measured by LA-ICP-MS. Results from both techniques were found to be in agreement with predictions from thermally activated, volume diffusion. However, outliers from the ID-TIMS data suggested some complexity, as grains were found to be too young relative to their diffusion radius. Interaction of multiple processes can be responsible for the alteration of apatite U-Pb dates such as: (1) metamorphic (over)growth, (2) fluid aided alteration/recrystallization and (3) metamictization and fracturing of the grain. Further, predictions from volume diffusion rely on the input parameters: (a) diffusivity, (b) activation energy and (c) shortest diffusion radius. Diffusivity and activation energy are potentially influenced by the chemical composition and subsequent changes in crystal structure. Currently there is one value for diffusion parameter and activation energy established for (Durango) apatite (Cherniak et al., 1991). Correlation between diffusivity/activation energy and composition has not been established. We investigate if correlations exist between diffusivity/activation energy and composition by obtaining single grain apatite U-Pb date and chemical compostion and correlating these to their diffusion radius. We test the consistency of apatite closure temperature, by comparing the apatite U-Pb dates with lower temperature thermochronometers such as white mica and K-feldspar Ar/Ar and by petrographic observations. We test if chemical information can be a proxy to identify

The Sr/Ca and Ba/Ca ratios in inorganic apatite are strongly dependent on the temperature of the aqueous medium during precipitation. If valid in biogenic apatite, these thermometers would offer the advantage of being more resistant to diagenesis than those calibrated on biogenic calcite and aragonite. We have reared seabreams ( Sparus aurata) in tanks with controlled conditions during experiments lasting for more than 2 years at 13, 17, 23 and 27 °C, in order to determine the variations in Sr and Ba partitioning relative to Ca ( DSr and DBa, respectively) between seawater and fish apatitic hard tissues (i.e. teeth and bones), as a function of temperature. The sensitivity of the Sr and Ba thermometers (i.e. ∂ DSr/∂ T and ∂ DBa/∂ T, respectively), are similar in bone ( ∂Db-wSr/∂ T = 0.0036 ± 0.0003 and ∂Db-wBa/∂ T = 0.0134 ± 0.0026, respectively) and enamel ( ∂De-wSr/∂ T = 0.0037 ± 0.0005 and ∂De-wBa/∂ T = 0.0107 ± 0.0026, respectively). The positive values of ∂ DSr/∂ T and ∂ DBa/∂ T in bone and enamel indicate that DSr and DBa increase with increasing temperature, a pattern opposite to that observed for inorganic apatite. This distinct thermodependent trace element partitioning between inorganic and organic apatite and water highlights the contradictory effects of the crystal-chemical and biological controls on the partitioning of Ca, Sr and Ba in vertebrate organisms. Taking into account the diet Sr/Ca and Ba/Ca values, it is shown that the bone Ba/Ca signature of fish can be explained by Ca-biopurification and inorganic apatite precipitation, whereas both of these processes fail to predict the bone Sr/Ca values. Therefore, the metabolism of Ca as a function of temperature still needs to be fully understood. However, the biogenic Sr thermometer is used to calculate an average seawater temperature of 30.6 °C using the Sr/Ca compositions of fossil shark teeth at the Cretaceous/Tertiary boundary, and a typical seawater Sr

In continuing search for effective treatments of cancer, the emerging model aims at efficient intracellular delivery of therapeutics into tumor cells in order to increase the drug concentration. However, the implementation of this strategy suffers from inefficient cellular uptake and drug resistance. Therefore, pH-sensitive nanosystems have recently been developed to target slightly acidic extracellular pH environment of solid tumors. The pH targeting approach is regarded as a more general strategy than conventional specific tumor cell surface targeting approaches, because the acidic tumor microclimate is most common in solid tumors. When nanosystems are combined with triggered release mechanisms in endosomal or lysosomal acidic pH along with endosomolytic capability, the nanocarriers demonstrated to overcome multidrug resistance of various tumors. Here, novel pH sensitive carbonate apatite has been fabricated to efficiently deliver anticancer drug Doxorubicin (DOX) to cancer cells, by virtue of its pH sensitivity being quite unstable under an acidic condition in endosomes and the desirable size of the resulting apatite-DOX for efficient cellular uptake as revealed by scanning electron microscopy. Florescence microscopy and flow cytometry analyses demonstrated significant uptake of drug (92%) when complexed with apatite nanoparticles. In vitro chemosensitivity assay revealed that apatite-DOX nanoparticles executed high cytotoxicity in several human cancer cell lines compared to free drugs and consequently apatite-DOX-facilitated enhanced tumor inhibitory effect was observed in colorectal tumor model within BALB/cA nude mice, thereby shedding light on their potential applications in cancer therapy. PMID:23613726

Current models of the temperature sensitivity of fission track annealing in apatites have been calibrated using fission track data from boreholes, with the assumption that these samples are currently at maximum burial depth and temperatures. The most detailed data-set comes from boreholes located in the Otway basin, Australia. However, several lines of evidence suggest that these samples are not at their maximum burial depth and temperature and consequently the cooling temperature of the apatite fission track thermochronometer would then be higher than previously assumed. Significant late Cenozoic exhumation in the Otway Basin was suggested by earlier studies that document a major late-Miocene erosional unconformity, folding and trusting of underlying sediments and elevated strandlines along the coast. In addition, anomalously young apatite (U-Th)/He ages in several boreholes in the basin suggest that the basin's sediments have been exhumed and cooled in the late Cenozoic. We explore the effects of late Cenozoic exhumation on fission track data in the Otway basin using a 1D model of burial and thermal history. We show that simulating several 100s of meters of exhumation in the basin results in significant misfit between current annealing models and observed fission track data. The additional exhumation reconciles the Otway basin data with a second detailed fission track dataset from boreholes in Southern Texas with a well-constrained thermal and burial history. We combine vitrinite reflectance data and U-Th/He data from the Otway basin to recalibrate the burial history of the Otway basin. Subsequently we combine the new thermal history of the Otway basin with the Southern Texas dataset to recalibrate the fission track annealing algorithm. The results suggest that fission-track annealing in apatites is underestimated by approximately 20°C by current annealing models, with significant implications for studies that use apatite fission track thermochronology to

Thermochronological data can constrain the cooling paths of rocks exhumed through the uppermost 1-2 km of earth's crust, and have thus been pivotal in illuminating topographic development over timescales >0.1 Ma. However, in some cases, different methods have led to conflicting conclusions about timing of valley-scale exhumation. Here, we investigate the case of Western Grand Canyon, USA, where different thermochronological datasets have been interpreted to record very different timings of canyon incision (∼70 Ma versus ∼5 Ma). We present a method to assess key assumptions in these constraints and demonstrate that burial heating conditions of basement rocks in the Mesozoic can result in incomplete annealing of radiation damage in apatite. In turn, this has a dramatic effect on the temperature sensitivity of the apatite (U-Th)/He system and its ability to record post-burial exhumation. The possibility of incomplete annealing resolves the apparent conflict in time-temperature paths inferred over the last 70 Ma, although it requires temperatures during burial that are lower than predicted by apatite fission track data. A refinement of parameters that prescribe the kinetics of damage annealing and related control on 4He diffusivity in apatite would account for this discrepancy, specifically if alpha recoil damage anneals at a lower rate than fission tracks at a given temperature. These effects will be important for any application of the apatite (U-Th)/He system in geologic settings that experienced prolonged residence (>10 Ma) between 50-150 °C; the approaches developed here provide means to assess these effects.

Different compositions of apatite-type La10Si6-xWxO27+δ ceramics are prepared successfully by the high-temperature solid state reaction route. Crystal structure and electrical properties of La10Si6-xWxO27+δ ceramics are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS). La10Si6-xWxO27+δ (x = 0.1, 0.2, 0.3, 0.4, 0.5) ceramics consist of a hexagonal apatite-type structure and a small amount of La6W2O15 phase of orthorhombic structure but no La2SiO5 phase. The diffraction peaks of the hexagonal apatite-type structure shift to the low angle side with doping the W6+. When the content of hexavalent tungsten is beyond 0.1, rod-like grains of La10Si6-xWxO27+δ ceramics are replaced gradually by equiaxed apatite-type grains, and some fine particles of La6W2O15 are observed at grain boundaries. These La6W2O15 particles are non-conducting materials and lead to the increase in grain impedance and grain boundary impedance of La10Si6-xWxO27+δ ceramics gradually when the content of hexavalent tungsten is beyond 0.2. However, the solid solubility of W6+ in the lattice of apatite-type structure reaches the maximum when the W6+ content is at 0.1, and correspondingly the La10Si5.9W0.1O27.1 ceramic has the highest total conductivity of 4.45 × 10-2 S cm-1 at 1073 K.

Using the method of scanning and high-resolution electron microscopy, the zones of indentation by scratching for apatite and quartz single crystals were investigated. The textural, structural and phase transformations revealed have been conventionally ascribed to “deformation” and “diffusion” processes of plastic deformation. In zones of indentation by scratching of single crystals there have been two levels of structural transformations revealed, with a sharp boundary between them, at a stress equal to the theoretical ultimate stress limit (σ{sub TSL}). In the top zone of scratches, within the range of stress from the microhardness value H{sub s} up to the σ{sub TSL} value the substance undergoes profound structural and phase transformations. In the bed of scratches at the stress value lower than σ{sub TSL} values, single crystal fragmentation occurs with the formation of blocks and steps.

Highly c-axis oriented apatite-type lanthanum silicate (LSO) thin films were fabricated by a simple solution coating method. In the solution coating method, LSO thin films are obtained by crystallization of initially deposited amorphous LSO precursor thin films. The degree of orientation was influenced by the precursor morphologies and a dense LSO precursor led to a high c-axis orientation perpendicular to the substrate. The oriented LSO thin films were composed of columnar grains with a single crystal orientation over the entire film thickness. In-plane orientation was not detected, which indicates that the c-axis orientation of the LSO thin films can be attributed to self-orientation. PMID:26391101

An experimental study in rats was done to investigate the bone-regenerating properties of collagen apatite (Collapat) and to compare it with osteoinduction dependent on osteogenin-containing gelatine (OCG). The test substances were implanted orthotopically (calvarial defect--7 mm in diameter) and heterotopically (paravertebral muscles, abdominal muscles). The results were evaluated histologically and enzymatically (alkaline phosphatase). Collapat caused neither osteoinduction in the heterotopic site nor healing of the bone defects. Foreign body reaction without new bone formation was encountered. OCG implantation leads to new bone formation in the muscles within 3 weeks, associated with a significant increase in alkaline phosphatase activity, and to extensive new bone formation in the calvarial defect within 4 weeks. The defects did not heal if left empty. The value of clinical application of Collapat appears to be doubtful. Osteoinduction with OCG requires further experimental investigation. PMID:3551878

Fish Canyon Tuff (FCT) is one of the most voluminous (>5,000 km3) ignimbrite eruptions documented on Earth. It erupted over a relatively short period from the ~80 km x 30 km La Garita caldera, San Juan volcanic field, Colorado and has served as an important source for geochronology standards, particularly for K-Ar, 40Ar/39Ar and fission track dating [e.g. 1-6]. Ar and U/Pb studies over many years to determine the age of FCT have resulted in disagreement [e.g. 3-5] and this has compromised the potential use of some FCT minerals as geochronology standards. However, a recent study, reporting an improved assessment of the 40K decay constants indicates a 40Ar/39Ar sanidine age of 28.305±0.036 Ma, which can also be reconciled with U/Pb zircon data [6]. In an effort to evaluate the suitability of FCT apatite as a standard for (U-Th-Sm)/He (AHe) thermochronometry we analysed samples from the lithic-rich classic site, some 8.7 km SW of South Fork, Colorado used for early fission track and Ar studies [1-2] and also from a ~330 m vertical section of FCT above that site. Average weighted mean AHe ages (±95% confidence level) from multiple analyses at five sites range from 20.5±1.5 Ma to 23.3±2.2 Ma. Apatite fission track (AFT) ages from the same samples determined by automated image capture and counting, in combination with LA-ICP-MS for U determination, range from 28.4±1.2 Ma at the classic site to 23.3±1.6 Ma at the top of the measured profile. AFT ages can be related to kinetic parameters Dpar and Cl content which are highest (2.19±0.3 μm and 0.73-0.87 wt % respectively) at the classic site, but vary through the profile. AHe and some AFT data provide strong evidence for substantial post-eruptive Early Miocene cooling of the FCT from temperatures estimated between >~80°C to ~110°C, and attributed to km-scale erosion, possibly triggered by structural changes related to formation of the nearby Rio Grande rift. Despite evidence for some later cooling, FCT apatite at

If the direct U-Pb dating of a fossil itself is possible, the method could have great impact on stratigraphic studies in establishing the absolute chronology of sedimentary sequences. Micro fossil ?conodont? are candidates for this purpose since they consist of apatite (Ca2(PO5)3 (F,Cl,OH)), which would uptake U, Th and Pb after sedimentation no longer than a few million years and is supposed to remain closed to U and Pb under relatively low effective closure temperature. We report here results of direct ion microprobe U-Th-Pb dating of two conodonts; Trichognathus from Kinderhookian stage of Mississippian sedimentary sequence from Illinois Basin region in North America and Panderodus from a Llandoverian sedimentary sequence on Langkawi Island, northern Malaysia. Secondary purpose of the study is to indicate in situ analysis of all REE on the same spots of U-Pb measurements. Samples were cast into epoxy resin discs with a few grains of standard apatite, PRAP, derived from an alkaline rock of Prairie Lake circular complex in the Canadian Shield and polished until they were exposed through their mid-sections. U, Th and REE abundances, and Pb isotopic compositions were measured by using SHRIMP installed at Hiroshima University. Thirteen spots on Trichognathus yield a 238U/206Pb isochron age of 323+/-36 Ma, which is consistent with the depositional and early diagenetic ages. Fifteen spots on Panderodus give 232Th/208Pb isochron age of 429+/-50 Ma, which is again comparable to an early Silurian. Shale-normalized REE of Trichognathus shows a broadly flat pattern from light to middle REE and a decrease from middle to heavy REE with negative anomalies of Ce and Eu. In contrast Panderodus indicates a concave-shape pattern with middle REE enrichment. These characteristics are probably due to a different formation environment as suggested by other workers.

La{sub 9.75}{open_square}{sub 0.25}(Ge{sub 6}O{sub 24})O{sub 2.62} oxy-apatite shows a phase transition from triclinic to hexagonal symmetry at approximately 1020 K that has been characterised by high-temperature synchrotron X-ray and neutron powder diffraction, and ionic conductivity measurements. The crystal structure at 1073 K has been determined from joint Rietveld refinements of synchrotron X-ray and neutron powder diffraction data. The study shows that hexagonal-La{sub 9.75}{open_square}{sub 0.25}(Ge{sub 6}O{sub 24})O{sub 2.62} contains interstitial oxygen at the position previously reported for other oxy-germanates. Changes in the oxide conductivity associated with this structural transition are discussed. The thermal analyses showed a weight loss on heating close to 600 K very likely due to water release. The synchrotron thermodiffractometric study shows an anomaly in the cell parameters evolution at that temperature, which indicates that this residual water is located into the apatite channels. The electrical characterisation under different atmospheres (dry and wet synthetic air) indicates that there is a significant proton contribution to the overall conductivity below 600 K, mainly under wet atmosphere. - Graphical abstract: La{sub 9.75}{open_square}{sub 0.25}(Ge{sub 6}O{sub 24})O{sub 2.62} oxide-conductor shows triclinic-hexagonal phase transition (see inset) at {approx}1020 K, meanwhile La{sub 9.55}{open_square}{sub 0.45}(Ge{sub 6}O{sub 24})O{sub 2.32} is hexagonal at all temperatures. Both compounds have mixed proton and oxide conductivities below 600 K.

This contribution investigates the interaction of two types of biomimetic-apatite colloidal nanoparticles (negatively-charged 47nm, and positively-charged 190nm NPs) with blood components, namely red blood cells (RBC) and plasma proteins, with the view to inspect their hemocompatibility. The NPs, preliminarily characterized by XRD, FTIR and DLS, showed low hemolysis ratio (typically lower than 5%) illustrating the high compatibility of such NPs with respect to RBC, even at high concentration (up to 10mg/ml). The presence of glucose as water-soluble matrix for freeze-dried and re-dispersed colloids led to slightly increased hemolysis as compared to glucose-free formulations. NPs/plasma protein interaction was then followed, via non-specific protein fluorescence quenching assays, by contact with whole human blood plasma. The amount of plasma proteins in interaction with the NPs was evaluated experimentally, and the data were fitted with the Hill plot and Stern-Volmer models. In all cases, binding constants of the order of 10(1)-10(2) were found. These values, significantly lower than those reported for other types of nanoparticles or molecular interactions, illustrate the fairly inert character of these colloidal NPs with respect to plasma proteins, which is desirable for circulating injectable suspensions. Results were discussed in relation with particle surface charge and mean particle hydrodynamic diameter (HD). On the basis of these hemocompatibility data, this study significantly complements previous results relative to the development and nontoxicity of biomimetic-apatite-based colloids stabilized by non-drug biocompatible organic molecules, intended for use in nanomedicine. PMID:27137807

Easily dissolved minerals such as calcite and apatite can be important in controlling stream and ground water chemistry even though these minerals are only present in trace amounts in granitoid rocks. Because of its solubility, apatite, a calcium phosphate mineral, may be a significant source of essential nutrients (especially phosphorous) for vegetation, and has been shown to strongly influence stream and soil water composition (e.g, calcium, strontium and rare earth elements). There are additional sources of Ca (e.g., feldspars, hornblende) and P (e.g., organic matter or bound to Fe and Al oxides) in granitoid soils. In order to distinguish the chemical constituents of apatite from other pools in the bulk soil, we selectively dissolved apatite with a dilute acid leach, and measured Pb isotopic ratios of apatite, feldspar, and leachates. We tested the leaching procedure on mineral separates and verified that a dilute nitric solution primarily dissolves apatite. Silicates were dissolved in subsequent steps by successively stronger acids. We then applied this method to bulk soils collected from several soil pits across a small watershed at the Hubbard Brook Experimental Forest (HBEF), New Hampshire, USA, to determine the spatial distribution of Ca and P pools, and determine the depth of apatite depletion in the soil. We also measured Pb isotope ratios in the soil leachates to distinguish among the various sources of Pb (e.g., apatite, feldspars and anthropogenic sources). We found that Pb in the dilute nitric leach of the HBEF organic soils is dominated by anthropogenic sources and that Pb from apatite becomes increasingly important with depth.

We present a new strategy on how to synthesize trace-element bearing (REE, Sr) chlorapatites Ca5(PO4)3Cl using the flux growth method. Synthetic apatites were up to several mm long, light blue in colour. The apatites were characterized using XRD, electron microprobe and laser ablation ICP-MS (LA-ICPMS) techniques and contained several hundred μg/g La, Ce, Pr, Sm, Gd and Lu and about 1700 μg/g Sr. The analyses indicate that apatites were homogenous (within the uncertainties) for major and trace elements. PMID:23531340

We present a new strategy on how to synthesize trace-element bearing (REE, Sr) chlorapatites Ca5(PO4)3Cl using the flux growth method. Synthetic apatites were up to several mm long, light blue in colour. The apatites were characterized using XRD, electron microprobe and laser ablation ICP-MS (LA-ICPMS) techniques and contained several hundred μg/g La, Ce, Pr, Sm, Gd and Lu and about 1700 μg/g Sr. The analyses indicate that apatites were homogenous (within the uncertainties) for major and trace elements. PMID:23531340

Hydrothermal experiments were conducted to determine the partitioning of Cl between rhyolitic to rhyodacitic melts, apatite, and aqueous fluid(s) and the partitioning of F between apatite and these melts at ca. 200 MPa and 900-924 °C. The number of fluid phases in our experiments is unknown; they may have involved a single fluid or vapor plus saline liquid. The partitioning behavior of Cl between apatite and melt is non-Nernstian and is a complex function of melt composition and the Cl concentration of the system. Values of DClapat/melt (wt. fraction of: Cl in apatite/Cl in melt) vary from 1 to 4.5 and are largest when the Cl concentrations of the melt are at or near the Cl-saturation value of the melt. The Cl-saturation concentrations of silicate melts are lowest in evolved, silica-rich melts, so with elevated Cl concentrations in a system and with all else equal, the maximum values of DClapat/melt occur with the most felsic melt. In contrast, values of DFapat/melt range from 11 to 40 for these felsic melts, and many of these are an order of magnitude greater than those applying to basaltic melts at 200 MPa and 1066-1150 °C. The Cl concentration of apatite is a simple and linear function of the concentration of Cl in fluid. Values of DClfluid/apat for these experiments range from 9 to 43, and some values are an order of magnitude greater than those determined in 200-MPa experiments involving basaltic melts at 1066-1150 °C. In order to determine the concentrations and interpret the behavior of volatile components in magmas, the experimental data have been applied to the halogen concentrations of apatite grains from chemically evolved rocks of Augustine volcano, Alaska; Krakatau volcano, Indonesia; Mt. Pinatubo, Philippines; Mt. St. Helens, Washington; Mt. Mazama, Oregon; Lascar volcano, Chile; Santorini volcano, Greece, and the Bishop Tuff, California. The F concentrations of these magmas estimated from apatite-melt equilibria range from 0.06 to 0.12 wt% and are

Marks et al. (2016) investigate the applicability of the Mn-in-apatite oxybarometer proposed by Miles et al. (2014) across a range of magma compositions using published data on well-characterised samples. The authors show that for magma compositions outside of the calc-alkaline and intermediate to silicic range used in the preliminary calibration, fO2 values calculated from Mn-in-apatite vary significantly from independently constrained estimates. These data are used to reiterate our warnings that other controls that are additional to oxygen fugacity are likely to affect Mn partitioning into apatite in some rock types, and particularly so in magmas that lie outside of the range of compositions and conditions used in the calibration. Marks et al. (2016) highlight that temperature may have an especially important effect on Mn partitioning in apatite in some rock types.

Martian meteorite Northwest Africa 7755 is a new example of an enriched, lherzolitic shergottite, containing some of the coarsest-grained apatite yet identified in shergottite meteorites. Their size has permitted detailed observations of volatile distributions within single grains. We have demonstrated that some apatites have been invaded by shock melts, which act to devolatilize parts of grains, resulting in significant Cl-enrichment in the adjacent regions. The extent of chemical heterogeneity within single grains must be carefully considered in other shergottites, so that the effects of secondary modification of apatites are well-constrained, prior to interpreting the volatile contents and primary magmatic processes. Apatite grains unaffected by shock melts are OH-F enriched and Cl-poor (∼F50Cl14OH36), relative to interstitial apatites reported in other shergottites. The volatile compositions are similar to interstitial apatites reported in terrestrial mafic intrusions. Such apatites in terrestrial intrusions are argued to have formed after significant Cl-loss due to the exsolution and migration of Cl-rich brines. Calculated relative F2, Cl2, and H2O fugacities for NWA 7755 apatites show a trend of degassing rather than fractionation, noted in previous studies. Indeed, we interpret the volatile contents of apatites analyzed in the cumulate shergottite NWA 7755 to represent snapshots of the evolving late-stage residual liquid during exsolution of a Cl-rich brine. This fluid phase has subsequently been lost from an open magma system, migrating upward through the cumulate sequence enriching residual liquids in Cl. Alternatively, it formed a hydrothermal system in the martian crust surrounding the intrusion. Furthermore, by comparison with terrestrial examples, we suggest that the late-stage evolution of volatile-bearing phases in NWA 7755 is similar to that of comparable terrestrial mafic rocks. Primary cumulus apatites are F-rich, whereas interstitial apatites

Reliable methods for direct dating of biogenic apatite from pre-Pleistocene fossils are currently not available, and recent attempts using the Lu-Hf decay system yielded highly inaccurate ages for both bones and teeth. The geological processes accounting for this poor accuracy of Lu-Hf chronometry are not yet understood. Here we explore Lu-Hf systematics in fossil bones and teeth in detail, by applying five different sample digestion techniques that are tested on bones and composites of bone and sediment. Our current dataset implies that dissolution methods only slightly affect the resulting Lu-Hf ages, while clear differences between the individual digestion techniques became apparent for element concentrations. By analysing the insoluble leftovers from incomplete sample dissolution, four main reservoirs of Hf in fossil bones were identified: (1) a radiogenic end-member associated with apatite; (2) an unradiogenic end-member represented by the authigenic minerals or the embedding sediment; (3) a highly unradiogenic end-member that can be attributed to detrital zircon; and (4) a moderately soluble phase (probably a Zr(Hf)-phosphate) that yielded very low Lu/Hf but a highly radiogenic Hf isotope composition at the same time. This Zr(Hf)-phase must have been precipitated within the fossil bone sample at a late stage of burial history, thereby incorporating radiogenic 176Hf released from apatite surfaces over geological timescales. A second focus of our study is the effect of different sediment matrices and of crystal size on the preservation of pristine Lu-Hf isotope compositions in bioapatite. Because near-depositional Lu-Hf ages of phosphate fossils have previously been reported for the London Clay (England) and a calcareous marl from Tendaguru (Tanzania), we herein investigate specimens fossilised in carbonate matrices (calcareous marl from Oker, Germany; carbonate concretions from the Santana Formation, Brazil; carbonate from the Eifel, Germany) and argillaceous

Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

Mechanisms governing phosphorus (P) speciation in coastal sediments remain largely unknown due to the diversity of coastal environments and poor analytical specificity for P phases. We investigated P speciation across salinity gradients comprising diverse ecosystems in a P-enriched estuary. To determine P load effects on P speciation we compared the high P site with a low P site. Octacalcium phosphate (OCP), authigenic apatite (carbonate fluorapatite, CFAP) and detrital apatite (fluorapatite) were quantitated in addition to Al/Fe-bound P (Al/Fe-P) and Ca-bound P (Ca-P). Gradients in sediment pH strongly affected P fractions across ecosystems and independent of the site-specific total P status. We found a pronounced switch from adsorbed Al/Fe-P to mineral Ca-P with decreasing acidity from land to sea. This switch occurred at near-neutral sediment pH and has possibly been enhanced by redox-driven phosphate desorption from iron oxyhydroxides. The seaward decline in Al/Fe-P was counterbalanced by the precipitation of Ca-P. Correspondingly, two location-dependent accumulation mechanisms occurred at the high P site due to the switch, leading to elevated Al/Fe-P at pH < 6.6 (landward; adsorption) and elevated Ca-P at pH > 6.6 (seaward; precipitation). Enhanced Ca-P precipitation by increased P loads was also evident from disproportional accumulation of metastable Ca-P (Ca-Pmeta) at the high P site. Here, sediments contained on average 6-fold higher Ca-Pmeta levels compared with the low P site, although these sediments contained only 2-fold more total Ca-P than the low P sediments. Phosphorus species distributions indicated that these elevated Ca-Pmeta levels resulted from transformation of fertilizer-derived Al/Fe-P to OCP and CFAP in nearshore areas. Formation of CFAP as well as its precursor, OCP, results in P retention in coastal zones and can thus lead to substantial inorganic P accumulation in response to anthropogenic P input.

We produced regenerative artificial bone material and bone parts using vacuum-sintered bodies of a novel apatite called "Titanium medical apatite (TMA®)" for biomedical applications. TMA was formed by chemically connecting a Ti oxide molecule with the reactive [Ca10(PO4)6] group of Hydroxyapatite (HAp). The TMA powders were kneaded with distilled water, and solid cylinders of compacted TMA were made by compression molding at 10 MPa using a stainless-steel vessel. The TMA compacts were dried and then sintered in vacuum (about 10-3 Pa) or in air using a resistance heating furnace in the temperature range 1073-1773 K. TMA compacts were sintered at temperatures greater than 1073 K, thus resulting in recrystallization. The TMA compact bodies sintered in the range 1273-1773 K were converted into mixtures composed of three crystalline materials: α-TCP (tricalcium phosphate), β-TCP, and Perovskite-CaTiO3. The Perovskite crystals were stable and hard. In vacuum-sintering, the Perovskite crystals were transformed into fibers (approximately 1 µm in diameter × 8 µm in length), and the fiber distribution was uniform in various directions. We refer to the TMA vacuum-sintered bodies as a "reinforced composite material with Perovskite crystal fibers." However, in atmospheric sintering, the Perovskite crystals were of various sizes and were irregularly distributed as a result of the effect of oxygen. After sintering temperature at 1573 K, the following results were obtained: the obtained TMA vacuum-sintered bodies (1) were white, (2) had a density of approximately 2300 kg/m3 (corresponding to that of a compact bone or a tooth), and had a thermal conductivity of approximately 31.3 W/(m·K) (corresponding to those of metal or ceramic implants). Further, it was possible to cut the TMA bodies into various forms with a cutting machine. An implant made of TMA and inserted into a rabbit jaw bone was covered by new bone tissues after just one month because of the high

We evaluate the effects of strontium ranelate on the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures, a system that gave us the advantage of obtaining mineral samples produced exclusively during treatment. Cells were treated with strontium ranelate at concentrations of 0.05 and 0.5 mM Sr(2+). Mineral substances were isolated and analyzed by using a combination of methods: Fourier transform infrared spectroscopy, solid-state (1)H nuclear magnetic resonance, X-ray diffraction, micro-Raman spectroscopy and energy dispersive X-ray spectroscopy. The minerals produced in all cell cultures were typical bone-like apatites. No changes occurred in the local structural order or crystal size of the minerals. However, we noticed several relevant changes in the mineral produced under 0.5 mM Sr(2+): (1) increase in type-B CO3 (2-) substitutions, which often lead to the creation of vacancies in Ca(2+) and OH(-) sites; (2) incorporation of Sr(2+) by substituting slightly less than 10 % of Ca(2+) in the apatite crystal lattice, resulting in an increase in both lattice parameters a and c; (3) change in the PO4 (3-) environments, possibly because of the expansion of the lattice; (4) the Ca/P ratio of this mineral was reduced, but its (Ca+Sr)/P ratio was the same as that of the control, indicating that its overall cation/P ratio was preserved. Thus, strontium ranelate changes the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures. PMID:24859219

Kerimasi calciocarbonatite consists principally of calcite together with lesser apatite, magnetite, and monticellite. Calcite hosts fluid and S-bearing Na-K-Ca-carbonate inclusions. Carbonatite melt and fluid inclusions occur in apatite and magnetite, and silicate melt inclusions in magnetite. This study presents statistically significant compositional data for quenched S- and P-bearing, Ca-alkali-rich carbonatite melt inclusions in magnetite and apatite. Magnetite-hosted silicate melts are peralkaline with normative sodium-metasilicate. On the basis of our microthermometric results on apatite-hosted melt inclusions and forsterite-monticellite phase relationships, temperatures of the early stage of magma evolution are estimated to be 900-1,000°C. At this time three immiscible liquid phases coexisted: (1) a Ca-rich, P-, S- and alkali-bearing carbonatite melt, (2) a Mg- and Fe-rich, peralkaline silicate melt, and (3) a C-O-H-S-alkali fluid. During the development of coexisting carbonatite and silicate melts, the Si/Al and Mg/Fe ratio of the silicate melt decreased with contemporaneous increase in alkalis due to olivine fractionation, whereas the alkali content of the carbonatite melt increased with concomitant decrease in CaO resulting from calcite fractionation. Overall the peralkalinity of the bulk composition of the immiscible melts increased, resulting in a decrease in the size of the miscibility gap in the pseudoquaternary system studied. Inclusion data indicate the formation of a carbonatite magma that is extremely enriched in alkalis with a composition similar to that of Oldoinyo Lengai natrocarbonatite. In contrast to the bulk compositions of calciocarbonatite rocks, the melt inclusions investigated contain significant amount of alkalis (Na2O + K2O) that is at least 5-10 wt%. The compositions of carbonatite melt inclusions are considered as being better representatives of parental magma composition than those of any bulk rock.

This paper presents the author's theory on the possibility of simultaneous hard-phase synthesis of various organic molecules from gas-phase elements on the basis of the apatite matrix and cocrystallizing minerals (carbonate-apatite, calcite, mica). These molecules and their ensembles gave rise to living systems and protocells of the pro- and eukaryotic types. Synthesis might have occurred through gradual substitution of the mineral matrix by crystal organic matter. The structure and size of the molecules synthesized were determined by the structure, physical parameters, and arrangement of organizing centers in the crystal lattice. Apatite phosphates were embedded in a synthesized nucleic helix and their size and purine-pyrimidine complementarity were determined. Apatite and cocrystallizing minerals were seen to be involved in the synthesis of four basic classes of cell components: apatite-DNA and nucleoproteide complexes; carbonate-apatite-enzymes, other proteins involved in DNA replication, all RNA types and their complexes with the specific proteins and enzymes of transcription and translation; calcite-cytoskeletal proteins; and mica-membrane lipids and proteins. The evidence supporting this theory is presented. A possible mechanism to account for the transition from crystal through organo-mineral crystal to liquid crystal (protocell) and a model of the occurrence of the matrix mechanism of transcription and translation are proposed. Some principal problems in the biochemistry and molecular biology of the origin of life on the Earth are discussed. PMID:23345922

Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca2+ ions and causes the formation of CaCit- and Ca10(PO4)6CO3 complexes. Trisodium citrate binds Ca2+ ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed.

The effect of calcium salt content in the poly(epsilon-caprolactone) (PCL)/silica nanocomposite on the nucleation and growth behavior of apatite layer in simulated body fluid (SBF) was investigated. The specimens were prepared with low (L) and high (H) concentrations of calcium nitrate tetrahydrate through a sol-gel method. After soaking in the SBF at 36.5 degrees C for 1 week, a densely packed apatite layer that had a smooth surface and a Ca/P ratio similar to bone was formed on specimens containing a low concentration of calcium salt while a loosely packed apatite layer with a rugged surface and a higher Ca/P ratio than that of bone occurred on specimens containing a high concentration of calcium salt. The results are explained in terms of the degree of supersaturation of apatite in the SBF, as determined by the concentrations of constituent ions of apatite and pH. The practical implication of the results is that a dense and bone-like apatite layer on the PCL/silica nanocomposite in vitro, and perhaps in vivo, can be achieved by adopting an appropriate calcium salt content. PMID:14624498

In this work, the bioactive glass 45S5 (also known by its commercial name Bioglass®) was successfully dip-coated by a natural derived biopolymer, increasing its apatite-forming ability. The biopolymer was shown to accelerate the first stages of bioactivity, inducing a fast transition to step 4 (formation of amorphous Casbnd P layer) in the apatite-forming ability mechanism. The faster precipitation of Ca/P crystals in the coated samples resulted in the formation of an intermediate amorphous octacalcium phosphate, which later transforms into an apatite layer with high thickness. The effect of the thickness of the coating was also studied on samples coated with polymer suspensions of different concentrations (0.15% and 1.5%, w/v), revealing that the kinetics of formation of the final hydroxycarbonate apatite layer increases with the thickness of the coating. The mechanism by which this apatite-forming ability is accelerated was also investigated, revealing that certain functional groups present in the structure of the polymer allow it to act as an organic matrix and preferential nucleation site for the growth of the hydroxycarbonate apatite layer.

To improve the biocompatibility, inter-connective pore structure, and drug delivery ability of self-setting apatite/collagen composite cement (ACC), a three-dimensionally perforated porous apatite/collagen composite cement (TPPACC) containing 3% indomethacin (IMC) was obtained in an arranged multi-cross with 20, 40, and 60 stainless steel needlelike male dies, and stored and hardened at 37 degrees C and 100% relative humidity for 24 h. The mean radius of micro-pores of the TPPACC was evaluated to be 0.125 microm by mercury porosimetry. X-ray powder diffraction and FT-IR spectroscopy suggested that TPPACC consisted of carbonated apatite and had a structure similar to that of natural rat bone. The IMC release rates from a TPPACC block containing the drug were measured in simulated body fluid. The rate of release increased with the number of macro-pores that from planar surface matrix systems followed the Higuchi equation. The relationship between the Higuchi constant and surface area of TPPACC showed a straight line with K = 0.2123 and R(2) = 0.9892. These results indicated that the rate of drug release from TPPACC could be controlled by the number of macro-pores for bone cells. PMID:19821491

Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

In this study, the tantalum oxide coatings were formed on pure tantalum (Ta) by micro-arc oxidation (MAO) in electrolytic solutions of calcium acetate and β-glycerophosphate disodium, and the effect of the applied voltage on the microstructure and bond strength of the MAO coatings was systematically investigated. The effect of annealing treatment on the microstructure, bond strength and apatite-inducing ability of the MAO coatings formed at 350 and 450 V was also studied. The study revealed that during the preparation of tantalum oxide coatings on Ta substrate by MAO, the applied voltage considerably affected the phase components, morphologies and bond strength of the coatings, but had little effect on surface chemical species. After annealing treatment, newly formed CaTa4O11 phase mainly contributed to the much more stronger apatite-inducing ability of the annealed tantalum oxide coatings than those that were not annealed. The better apatite-inducing ability of the MAO coatings formed at 450 V compared to those formed at 350 V was attributed to the less amorphous phase and more crystalline phase as well as more Ca and P contained in the MAO coatings with increasing the applied voltage.

The role of oligo-elements such as Zn in the genesis of pathological calcifications is widely debated in the literature. An essential element of discussion is given by their localization either at the surface or within the Ca apatite crystalline network. To determine the localization, X-ray absorption experiments have been performed at SOLEIL. The Exafs results suggest that Zn atoms, present in the Zn{sup 2+} form, are bound to about 4 O atoms at a distance of 2.00{angstrom}, while the interatomic distance R{sub CaO} ranges between 2.35 {angstrom} and 2.71 {angstrom}. Taking into account the content of Zn (around 1000 ppm) and the difference in ionic radius between Zn{sup 2+} (0.074 nm) and Ca{sup 2+} (0.099 nm), a significant longer interatomic distance would be expected in the case of Zn replacing Ca within the apatite crystalline network. We thus conclude that Zn atoms are localized at the surface and not in the apatite nanocrystal structure. Such structural result has essential biological implications for at least two reasons. Some oligoelements have a marked effect on the transformation of chemical phases, and may modify the morphology of crystals. These are both major issues because, in the case of kidney stones, the medical treatment depends strongly on the precise chemical phase and on the morphology of the biological entities at both macroscopic and mesoscopic scales.

This study investigated the use of tailings from apatite ore beneficiation in the remediation of a heavily contaminated shooting range soil. The tailings originating in Siilinjärvi carbonatite complex, Finland, consist of apatite residues accompanied by phlogopite and calcite. In a pot experiment, organic top layer of a boreal forest soil predisposed to pellet-derived lead (Pb) was amended with tailings of various particle-sizes (Ø>0.2mm, Ø<0.2mm and unsieved material) differing in their mineralogical composition. After 9-, 10-, 14- and 21-month incubation, the samples were monitored for tailings-induced changes in the different Pb pools by means of sequential fractionation. Following the incubation, the samples were extracted with water and the extracts were analyzed for Pb species distribution by means of a cation exchange resin. The results revealed that Pb was continuously released from the shotgun pellet fragments due to weathering. However, the apatite and calcite compartments in the tailings counteracted the mobility of the released Pb through the formation of sparingly soluble fluorpyromorphite and cerussite. Furthermore, the tailings efficiently reduced the bioavailability of Pb by transferring it from the water-soluble and exchangeable pools into the organic one. The material also increased the proportion of the less toxic non-cationic Pb to the total dissolved Pb from the initial level of 5% to 9-12%. The results suggest that the tailings-induced stabilization of Pb may be an environmentally sound remediation technique at polluted sites. PMID:21871651

Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. PMID:27379398

This study was aimed at evaluating the physico-chemical properties of a porous poly(ɛ-caprolactone)/carbonated-apatite (PCL/CAp 30/70 w/w) composite to be used as scaffold for bone tissue engineering. The in vitro degradation mechanism of this matrix in different media was evaluated as well as its bioactivity in a simulated body fluid (SBF) buffered at pH 7.4 (37 °C, 28 days). For this purpose, we used vibrational IR and Raman spectroscopy coupled to thermogravimetry (TG) and differential scanning calorimetry (DSC). The samples were analyzed before and after immersion in the above mentioned solution as well as in 0.01 M NaOH solution (pH=12), saline phosphate buffer at pH 7.4 (SPB) and esterase/SPB. A control PCL sample was analyzed before the addition of the apatitic component. As regards the untreated samples, the method of synthesis utilized for preparing the composite was found to lower the crystallinity degree. The CAp component revealed to be constituted of a B-type CAp with a 3% carbonate content. After immersion in SBF solution, vibrational analysis coupled to TG revealed the deposition of a significant amount of an apatite component on the surface of the PCL/CAp composite as well as in its interior, showing a good in vitro mineralization.

Oxygen isotope ratios of mineralized structures in fish reflect the temperature and isotopic composition of the water in which they grow. For bulk samples (e.g., whole scales, bones, and otoliths), understanding how this signal is integrated across time and space is critical, especially for organisms exposed to high variability in growth conditions. Here, we assess the response of fish scale δ18O (from apatite phosphate) to experimentally manipulated water conditions. Wild-caught sardines were grown at controlled temperatures (13°C, 17°C, and 21°C) for 11 months. Higher growth temperatures correlated to lower δ18O values, representing a combination of scale apatite deposited before and after the temperature manipulation. Models that account for both biomineral allometry and exposure to varying water properties (e.g., by overlaying migration routes, isoscapes, and temperature maps) have the potential to quantify the varying contributions of minerals grown under different conditions. We use this method to predict δ18O of apatite phosphate for small pelagic fish found in California coastal waters, then compare expected values to those obtained from collected samples. Since phosphate oxygen is relatively resistant to diagenesis, this modern calibration establishes a framework for paleo studies.

Eclogite mantle xenoliths from the central part of Siberian craton (Udachnaya and Zarnitsa kimberlite pipes) as well as from the northeastern edge of the craton (Obnazhennaya kimberlite) were studied in detail. Garnet and clinopyroxene show evident exsolution textures. Garnet comprises rutile, ilmenite, apatite, and quartz/coesite oriented inclusions. Clinopyroxene contains rutile (± ilmenite) and apatite precipitates. Granular inclusions of quartz in kyanite and garnet usually retain features of their high-pressure origin. According to thermobarometric calculations, the studied eclogitic suite was equilibrated within lithospheric mantle at 3.2-4.9 GPa and 813-1080 °C. The precursor composition of garnets from Udachnaya and Zarnitsa eclogites suggests their stability at depths 210-260 km. Apatite precipitation in clinopyroxenes of Udachnaya and Zarnitsa allows us to declare that original pyroxenes could have been indicative of their high P-T stability. Raman spectroscopic study of quartz and coesite precipitates in garnet porphyroblasts confirms our hypothesis on the origin of the exsolution textures during pressure-temperature decrease. With respect to mineralogical data, we suppose the rocks to be subjected to stepwise decompression and cooling within mantle reservoir.

The use of yttria stabilized zirconia (YSZ) as biomedical implants is often offset by its bioinert nature that prevents its osseointegration to occur. Therefore, the functionalization of YSZ surface by polydopamine to facilitate the biomineralization of apatite layer on top of the coated film has incessantly been studied. In this study YSZ discs were first immersed in 2 mg/mL of stirred dopamine solution at coating temperatures between 25 and 80 °C. The specimens were then incubated for 7d in 1.5 SBF. The effect of coating temperature on the properties (chemical compositions and wettability) and the apatite mineralization on top of the generated films was investigated. It was found that at 50 °C, the specimen displayed the highest intensity of Ca 2p peak (1.55 ± 0.42 cps) with Ca/P ratio of 1.67 due to the presence of abundant quinone groups (Cdbnd O). However, the hydrophilicity (40.9 ± 01.7°) was greatly improved at 60 °C accompanied by the highest film thickness of 306 nm. Therefore, it was concluded that the presence of high intensity of quinone groups (Cdbnd O) in polydopamine film at elevated temperature affects the chelation of Ca2+ ions and thus enhance the growth of apatite layer on top of the functionalized YSZ surface.

The aim of this study was to evaluate the bone tissue response to strontium- and silicon-substituted apatite (Sr-HA and Si-HA) modified titanium (Ti) implants. Sr-HA, Si-HA and HA were grown on thermally oxidized Ti implants by a biomimetic process. Oxidized implants were used as controls. Surface properties, i.e. chemical composition, surface thickness, morphology/pore characteristics, crystal structure and roughness, were characterized with various analytical techniques. The implants were inserted in rat tibiae and block biopsies were prepared for histology, histomorphometry and scanning electron microscopy analysis. Histologically, new bone formed on all implant surfaces. The bone was deposited directly onto the Sr-HA and Si-HA implants without any intervening soft tissue. The statistical analysis showed significant higher amount of bone–implant contact (BIC) for the Si-doped HA modification (P = 0.030), whereas significant higher bone area (BA) for the Sr-doped HA modification (P = 0.034), when compared with the non-doped HA modification. The differences were most pronounced at the early time point. The healing time had a significant impact for both BA and BIC (P < 0.001). The present results show that biomimetically prepared Si-HA and Sr-HA on Ti implants provided bioactivity and promoted early bone formation. PMID:22279159

Electron microprobe analyses are presented for fluorapatite phenocrysts from a benmoreite-peralkaline rhyolite volcanic suite from the Kenya Rift Valley. The rocks have previously been well characterized petrographically and their crystallization conditions are reasonably well known. The REE contents in the M site increase towards the rhyolites, with a maximum britholite component of ~35 mol.%. Chondrite-normalized REE patterns are rather flat between La and Sm and then decrease towards Yb. Sodium and Fe occupy up to 1% and 4%, respectively, of the M site. The major coupled substitution is REE3+ + Si4+ ??? Ca2+ + P5+. The substitution REE3+ + Na+ ??? 2Ca2+ has been of minor importance. The relatively large Fe contents were perhaps facilitated by the low fo2 conditions of crystallization. Zoning is ubiquitous and resulted from both fractional crystallization and magma mixing. Apatites in some rhyolites are relatively Y-depleted, perhaps reflecting crystallization from melts which had precipitated zircon. Mineral/glass (melt) ratios for two rhyolites are unusually high, with maxima at Sm (762, 1123). ?? 2008 The Mineralogical Society.

Marine phosphorites are predominantly composed of carbonated fluorapatite (CFA = Ca10‑a‑b‑cNaaMgb(PO4)6‑x(CO3)x‑y‑z(CO3.F)y(SO4)zF2, where x=y+a+2c, and c represents the number of Ca vacancies, with a P2O5 content that ranges from 18-40 %. Sulphur-oxidizing bacteria of the Beggiatoa genus concentration phosphorous as intracellular polyphosphate ((PO3‑)n) which is depolymerized into inorganic orthophosphate (Pi). Consequently, an increase in pore water Pi concentration favours carbonated apatite precipitation. The carbonate and fluoride that is characteristic of phosphorite CFA is also located in the vertebrate skeleton. This similarity suggests a biochemical pathway for CFA precipitation. Preliminary Raman spectroscopy and powder x-ray diffraction results that suggest a role for fluoride, and possibly carbonate, in the biochemical depolymerisation of polyphosphates with alkaline phosphatase will be presented.

Biomimetic calcium phosphate (Ca-P) coatings were applied onto dense titanium alloy (Ti6Al4V) and porous tantalum (Ta) cylinders by immersion into simulated body fluid at 37 degrees C and then at 50 degrees C for 24 h. As a result, a homogeneous bone-like carbonated apatitic (BCA) coating, 30 microm thick was deposited on the entire surface of the dense and porous implants. Noncoated and BCA-coated implants were press-fit implanted in the femoral diaphysis of 14 adult female goats. Bone contact was measured after implantation for 6, 12, and 24 weeks, and investigated by histology and backscattered electron microscopy (BSEM). After 6 weeks, bone contact of the BCA-coated Ti6Al4V implants was about 50%. After 12 and 24 weeks, bone contact was lower in comparison with the 6-week implantations at, respectively 24 and 39%. Regarding the BCA-coated porous Ta implants, bone contacts were 17, 30, and 18% after 6, 12, and 24 weeks, respectively. However, bone contact was always found significantly higher for BCA-coated dense Ti6Al4V and porous Ta cylinders than the corresponding noncoated implants. The results of this study show that the BCA coating enhances the bone integration as compared to the noncoated implants. PMID:14528464

We have developed bone cement introducing Strontium (Sr) to promote early bone regeneration. To prolong the release duration of Sr, we applied inorganic Sr filler for containing into the cement powder. The purpose of this study is to evaluate the mechanical properties, crystallinic properties, and ion release activities, especially Sr anion, of this cement. Alpha-TCP powder was mixed with Sr filler, with 0.1wt%, 0.5wt%, 1.0wt%, and 5.0wt%. These were mixed with mixing liquid and formed for each test. They were incubated and crystalized in 95% moisture for 1 week. The mechanical properties were studied by the compression, the diametral tensile strength and 4-point vending. Tested specimens were evaluated by X-ray diffraction(XRD) and scanning electron microscopic(SEM) imaging. The ion release behaviors were measured by inductively coupled plasma mass spectrometry(ICP-MS). The mechanical properties were increased in consistency of filler, but decreased in some samples because of declining the apatite matrix. And the Sr release showed interesting results as the sequential resource of Sr. By adjusting the mixing ratio or considering the application of these Sr releasable cements, this material would show good performance by its strength and longer Sr release for bone regeneration. PMID:24109823

Apatite- and tricalcium phosphate-based materials were produced from codfish bones, thus converting a waste by-product from the food industry into high added-valued compounds. The bones were annealed at temperatures between 900 and 1200 °C, giving a biphasic material of hydroxyapatite and tricalcium phosphate (Ca10(PO4)6(OH)2 and β-Ca(PO4)3) with a molar proportion of 75:25, a material widely used in biomedical implants. The treatment of the bones in solution prior to their annealing changed the composition of the material. Single phase hydroxyapatite, chlorapatite (Ca10(PO4)6Cl2) and fluorapatite (Ca10(PO4)6F2) were obtained using CaCl2 and NaF solutions, respectively. The samples were analysed by several techniques (X-ray diffraction, infrared spectroscopy, scanning electron microscopy and differential thermal/thermogravimetric analysis) and by elemental analyses, to have a more complete understanding of the conversion process. Such compositional modifications have never been performed before for these materials of natural origin to tailor the relative concentrations of elements. This paper shows the great potential for the conversion of this by-product into highly valuable compounds for biomedical applications, using a simple and effective valorisation process. PMID:25428050

Single crystals of the title compound, strontium tetra-praseo-dymium tris-(silicate) oxide, SrPr(4)(SiO(4))(3)O, have been grown by the self-flux method using SrCl(2). The structure is isotypic with the apatite supergroup family having the generic formula (IX)M1(2) (VII)M2(3)((IV)TO(4))(3)X, where M = alkaline earth and rare earth metals, T = Si and X = O. The M1 site (3.. symmetry) is occupied by Pr and Sr atoms with almost even proportions and is surrounded by nine O atoms forming a tricapped trigonal prism. The M2 site (m.. symmetry) is almost exclusively occupied by Pr and surrounded by seven O atoms, forming a distorted penta-gonal bipyramid. The Si atom (m.. symmetry) is surrounded by two O (m.. symmetry) and two O atoms in general positions, forming an isolated SiO(4) tetra-hedron. Another O atom at the inversion centre (.. symmetry) is surrounded by three M2 sites, forming an equilateral triangle perpendicular to the c axis. PMID:21588475

RNA interference (RNAi) technology is currently being tested in clinical trials for a limited number of diseases. However, systemic delivery of small interfering RNA (siRNA) to solid tumors has not yet been achieved in clinics. Here, we introduce an in vivo pH-sensitive delivery system for siRNA using super carbonate apatite (sCA) nanoparticles, which is the smallest class of nanocarrier. These carriers consist simply of inorganic ions and accumulate specifically in tumors, yet they cause no serious adverse events in mice and monkeys. Intravenously administered sCA-siRNA abundantly accumulated in the cytoplasm of tumor cells at 4 h, indicating quick achievement of endosomal escape. sCA-survivin-siRNA induced apoptosis in HT29 tumors and significantly inhibited in vivo tumor growth of HCT116, to a greater extent than two other in vivo delivery reagents. With innovative in vivo delivery efficiency, sCA could be a useful nanoparticle for the therapy of solid tumors. PMID:25738937

The fabrication and characterization of a carbonate-containing apatite film deposited on a Ti plate via an aqueous spray method is described. The mist of the spray solution emitted from a perpendicularly oriented airbrush was made to strike a warmed Ti substrate. The thicknesses of the sprayed film and those heat-treated at 400 °C-700 °C under Ar gas flow were in the range 1.21-1.40 μm. The results of elemental analyses and Fourier transform infrared spectroscopy of the powders that were mechanically collected from the surface of the sprayed film suggest that the film was Ca(10)(PO4)6(CO3) · 2CO2 · 3H2O. The presence of the carbonate ion and the lattice CO2 molecule was confirmed via the aforementioned analyses; the finding was also consistent with the X-ray diffraction patterns of the films and the chemical identity of the sprayed and heat-treated films that were measured using X-ray photoelectron spectroscopy. The sprayed film comprises a characteristic network structure, which contains round particles within the networks, as was observed by field-emission scanning electron microscopy. A scratch test indicated that the shear stress of the sprayed film (21 MPa) significantly improved to 40 and >133 MPa after heat-treatment at 600 °C and 700 °C, respectively, under Ar gas flow for 10 min. PMID:25427510

There have been several attempts to combine bioactive glasses (BaGs) with biodegradable polymers to create a scaffold material with excellent biocompatibility, bioactivity, biodegradability and toughness. In the present study, the nanocomposite scaffolds with compositions based on gelatin (Gel) and BaG nanoparticles in the ternary SiO 2-CaO-P 2O 5 system were prepared. In vitro evaluations of the nanocomposite scaffolds were performed, and for investigating their bioactive capacity these scaffolds were soaked in a simulated body fluid (SBF) at different time intervals. The scaffolds showed significant enhancement in bioactivity within few days of immersion in SBF solution. The apatite formation at the surface of the nanocomposite samples confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray powder diffraction (XRD) analyses. In vitro experiments with osteoblast cells indicated an appropriate penetration of the cells into the scaffold's pores, and also the continuous increase in cell aggregation on the bioactive scaffolds with increase in the incubation time demonstrated the ability of the scaffolds to support cell growth. The SEM observations revealed that the prepared scaffolds were porous with three dimensional (3D) and interconnected microstructure, pore size was 200-500 μm and the porosity was 72-86%. The nanocomposite scaffold made from Gel and BaG nanoparticles could be considered as a highly bioactive and potential bone tissue engineering implant.

We have used the additive manufacturing technology of selective laser sintering (SLS), together with post SLS heat treatment, to produce porous three dimensional scaffolds from the glass-ceramic apatite-wollastonite (A-W). The A-W scaffolds were custom-designed to incorporate a cylindrical central channel to increase cell penetration and medium flow to the center of the scaffolds under dynamic culture conditions during in vitro testing and subsequent in vivo implantation. The scaffolds were seeded with human bone marrow mesenchymal stromal cells (MSCs) and cultured in spinner flasks. Using confocal and scanning electron microscopy, we demonstrated that MSCs formed and maintained a confluent layer of viable cells on all surfaces of the A-W scaffolds during dynamic culture. MSC-seeded, with and without osteogenic pre-differentiation, and unseeded A-W scaffolds were implanted subcutaneously in MF1 nude mice where osteoid formation and tissue in-growth were observed following histological assessment. The results demonstrate that the in vivo biocompatibility and osteo-supportive capacity of A-W scaffolds can be enhanced by SLS-custom design, without the requirement for osteogenic pre-induction, to advance their potential as patient-specific bone replacement materials. PMID:25777813

Objectives. This study aims at examining the ultrastructure of bone-derived biological apatite (BAp) from a series of small vertebrates and the effect of thermal treatment on its physiochemical properties. Materials and Methods. Femurs/fin rays and vertebral bodies of 5 kinds of small vertebrates were firstly analyzed with X-ray microtomography. Subsequently, BAp was obtained with thermal treatment and low power plasma ashing, respectively. The properties of BAp, including morphology, functional groups, and crystal characteristics were then analyzed. Results. The bones of grouper and hairtail were mainly composed of condensed bone. Spongy bone showed different distribution in the bones from frog, rat, and pigeon. No significant difference was found in bone mineral density of condensed bone and trabecular thickness of spongy bone. Only platelet-like crystals were observed for BAp obtained by plasma ashing, while rod-like and irregular crystals were both harvested from the bones treated by sintering. A much higher degree of crystallinity and larger crystal size but a lower content of carbonate were detected in the latter. Conclusion. Platelet-like BAp is the common inorganic component of vertebrate bones. BAp distributing in condensed and spongy bone may exhibit differing thermal reactivity. Thermal treatment may alter BAp's in vivo structure and composition. PMID:25695088

Bioactive glasses, particularly Bioglass® 45S5, have been used to clinically regenerate human bone since the mid-1980s; however, they show a strong tendency to undergo crystallization upon heat treatment, which limits their range of applications. Attempts at improving their processing (by reducing their tendency to crystallize) have included increasing their silica content (and thus their network connectivity), incorporating intermediate oxides or reducing their phosphate content, all of which reduce glass bioactivity. Therefore, bioactive glasses known for their good processing (e.g. 13-93) are considerably less bioactive. Here, we investigated if the processing of 45S5 bioactive glass can be improved while maintaining its network connectivity and phosphate content. The results show that, by increasing the calcium:alkali cation ratio, partially substituting potassium for sodium (thereby making use of the mixed alkali effect) and adding small amounts of fluoride, bioactive glasses can be obtained which have a larger processing window (suggesting that they can be processed more easily, allowing for sintering of scaffolds or drawing into fibres) while degrading readily and forming apatite in aqueous solution within a few hours. PMID:24880003

Apparent apatite fission-track ages from drill core penetrating basement on the flank of the Transcontinental Arch in northwestern Iowa range from 934 ?? 86 to 641 ?? 90 Ma. These ages, the oldest reported in North America, record at least two thermal events. The 934 Ma age, which is synchronous with KAr ages in the Grenville Province and many KAr whole-rock and RbSr isochron ages from the Lake Superior region, may document basement cooling caused by regional uplift and erosion of the crust. The remaining fission-track ages are products of a more recent thermal event, relative to the age of the samples, which raised temperatures into the zone of partial annealing. Heating may have occurred between the Middle Ordovician and Middle Cretaceous by burial of the basement with additional sediment. It is estimated that burial raised temperatures in the part of the basement sampled by the core to between 50 and 75??C. These temperature estimates imply paleogeothermal gradients of about 20??C/km, approximately two and one-half times present-day values, and burial of the basement by an additional 2-3 km of sediment. ?? 1986.

Iron is the most important metal for modern industry and Sweden is by far the largest iron-producer in Europe, yet the genesis of Sweden's main iron-source, the ‘Kiruna-type’ apatite-iron-oxide ores, remains enigmatic. We show that magnetites from the largest central Swedish ‘Kiruna-type’ deposit at Grängesberg have δ18O values between −0.4 and +3.7‰, while the 1.90−1.88 Ga meta-volcanic host rocks have δ18O values between +4.9 and +9‰. Over 90% of the magnetite data are consistent with direct precipitation from intermediate to felsic magmas or magmatic fluids at high-temperature (δ18Omgt > +0.9‰, i.e. ortho-magmatic). A smaller group of magnetites (δ18Omgt ≤ +0.9‰), in turn, equilibrated with high-δ18O, likely meteoric, hydrothermal fluids at low temperatures. The central Swedish ‘Kiruna-type’ ores thus formed dominantly through magmatic iron-oxide precipitation within a larger volcanic superstructure, while local hydrothermal activity resulted from low-temperature fluid circulation in the shallower parts of this system. PMID:23571605

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U

The Panzhihua layered intrusion in the ~ 260 Ma Emeishan large igneous province is composed of melagabbro and Fe-Ti oxide ore bodies in the lower zone (LZ) and the lower part of the middle zone (MZa), and Fe-Ti oxide-poor leucogabbro in the upper part of the middle zone (MZb) and upper zone (UZ). Cumulus apatite grains occur in the ~ 500- to 600-m-thick MZb, which makes up 25-30% of the ~ 2-km-thick intrusion. Apatite grains from the MZb show two compositional reversals in the composition of Sr, which divide the MZb into three sub-units from the base upwards, MZb1, MZb2 and MZb3. There is 1-3 vol.% apatite in the MZb1 and MZb2 and 2-5 vol.% apatite in the MZb3. Both apatite and plagioclase have an overall trend of decreasing Sr in each sub-unit. Most apatite grains from the MZb1 and MZb2 have negative Eu anomalies (Eu/Eu* = 0.70-0.98) on chondrite-normalized REE plots and some at the top of the MZb2 have positive Eu anomalies (Eu/Eu* = 1.09-1.18), whereas all grains from the MZb3 have positive Eu anomalies (Eu/Eu* = 1.11-1.25). We consider that the Panzhihua intrusion formed due to immiscibility of ferrobasaltic magmas in a large convection cell at high temperatures. The immiscible Fe-rich melt tended to move towards the base of the chamber, whereas the Si-rich melt moved upwards due to density differences. Crystallization of Fe-Ti oxides from the Fe-rich melt at high temperatures may result in the enrichment of P in the residual magmas. The upward moving residual P-rich magmas may have mixed with Si-rich melt to form a P- and Si-rich melt in the upper part of the chamber, from which the MZb formed. Double-diffusive convection circulated in the P- and Si-rich melt to form stratified magma layers. Magma mixing between the stratified magma layers resulted in the compositional reversals of apatite along the boundaries. Negative Eu anomaly of apatite in the MZb1 and MZb2 is attributed to prior crystallization of plagioclase, whereas replenishment of a syenitic magma to

The concentration of halogens in apatite, biotite and amphibole is investigated for a large variety of mantle-derived plutonic rocks (gabbros, diorites, monzonites, olivine- and pyroxene-bearing monzonitic to granitic rocks, syenites, carbonatites and a phoscorite). In all rocks studied, apatite occurs as an early magmatic phase, whereas biotite and amphibole may occur either as a late magmatic phase or as late-stage, potentially hydrothermal product replacing precursor olivine, pyroxene and Fe-Ti oxides (ilmenite and magnetite). Based on electron microprobe analyses for F and Cl and detailed textural observations, we test existing models of halogen partitioning between apatite and biotite. Bromine concentration data for apatite, biotite and amphibole are used to further refine our understanding of the geochemical similarities and differences between Cl and Br during magmatic and hydrothermal processes. Our data suggests that F and Cl contents in apatite, biotite and amphibole can indeed be useful monitors of the halogen systematics in magmas, but they may also be subject to post-magmatic changes to variable extents. The relatively small radius and compatible F cation seems to be less prone to post-magmatic alteration and is likely to best reflect the original magmatic halogen abundances - especially in apatite. However, the larger and probably more incompatible Cl anion, is more easily re-mobilized as reflected by strong redistribution of Cl in biotite and amphibole which have been clearly overprinted by hydrothermal fluids. In certain cases, the ability of halogens to re-distribute themselves after magmatic equilibrium partitioning (as emphasized by our data) suggests that observed partitioning (especially between apatite and biotite) may also be used as a very sensitive indicator for post-magmatic hydrothermal processes.

Apatite-mullite glass-ceramics are materials prepared by the controlled heat-induced devitrification of glasses of suitable composition and are under investigation for applications in dentistry and orthopaedics. The glasses used here are based on a system with the composition 1.5(5- x)SiO 2·(5- x)Al 2O 3·1.5P 2O 5·(5- x)CaO· xCaF 2. The amount of fluorine in the glasses was varied to investigate the crystallisation behaviour as a function of both fluorine content and temperature. The resultant crystalline phases are fluorapatite [Ca 10(PO 4) 6F 2], mullite [Al 6Si 2O 13] and in some cases, anorthite [CaAl 2Si 2O 8]. Crystal phases were identified using X-ray diffraction (XRD) from both the surface and the bulk of heat-treated monolithic samples and scanning electron microscopy (SEM) was used to image the crystal phase morphologies. Crystallisation characteristics varied widely in terms of apparent nucleation mechanism, crystal phases formed and microstructure. In general, glasses with higher fluorine content devitrified more readily to fluorapatite (FAp) with a higher nucleation density and for glasses with an intermediate to low fluorine content there tended to be an interdependence between FAp and mullite crystallisation. A greater tendency towards anorthite formation, especially at surfaces, was observed for glasses with lower fluorine contents. Furthermore, on decreasing the fluorine content, glasses tended to crystallise by formation of FAp spherulites with increasing diameter and with greater crystal aspect ratio.

Fibrin gels are a promising material for use in promoting bone repair and regeneration due to their ease of implant formation, tailorability, biocompatibility, and degradation by natural processes. However, these materials lack necessary osteoconductivity to nucleate calcium, integrate with surrounding bone, and promote bone formation. Polymeric substrata formed from poly(lactide-co-glycolide) (PLG) are widely used in bone tissue engineering. A carbonated apatite layer of bone-like mineral can be successfully grown on the surface of PLG microspheres after a multiday incubation process in modified simulated body fluid. Such coatings improve the osteoconductivity of the polymer, provide nucleation sites for cell-secreted calcium, and enhance the potential osseointegration with host tissue. We examined the capacity of mineralized polymeric microspheres suspended within fibrin hydrogels to enhance the osteoconductivity of fibrin gels and increase the osteogenic potential of these materials. The inclusion of microparticles, both nonmineralized and mineralized, reduced the capacity of mesenchymal stem cells (MSCs) to contract the gel. When cultured in osteogenic media, we detected a near linear increase in both calcium and phosphate incorporation in gels containing mineralized microspheres and entrapped MSCs. The osteoconductivity of acellular fibrin gels with mineralized and nonmineralized microspheres was assessed in a rodent calvarial bone defect over 12 weeks. Compared to untreated rodent calvarial bone defects, we detected significant increases in early vascularization when treated with fibrin gels, with greater vascularization, on average, occurring with gels containing microspheres. We detected a trend for increased bone mineral density in gels containing mineralized microspheres after 12 weeks. These findings demonstrate that the osteoconductivity of fibrin gels can be increased by inclusion of mineralized microspheres, but additional signals may be required to

Only a few studies have been reported on the stability and heavy metal distribution of soil aggregates after soil treatments to reduce the availability of heavy metals. In this study, apatite (22.3 t ha(-1)), lime (4.45 t ha(-1)), and charcoal (66.8 t ha(-1)) were applied to a heavy metal-contaminated soil for 4 years. The stability and heavy metal distribution of soil aggregates were investigated by dry and wet sieving. No significant change in the dry mean weight diameter was observed in any treatments. Compared with the control, three-amendment treatments significantly increased the wet mean weight diameter, but only charcoal treatment significantly increased the wet aggregate stability. The soil treatments increased the content of soil organic carbon, and the fraction 0.25-2 mm contained the highest content of soil organic carbon. Amendments' application slightly increased soil total Cu and Cd, but decreased the concentrations of CaCl2 -extractable Cu and Cd except for the fraction <0.053 mm. The fractions >2 and 0.25-2 mm contained the highest concentrations of CaCl2-extractable Cu and Cd, accounted for about 74.5-86.8 % of CaCl2-extractable Cu and Cd in soil. The results indicated that amendments' application increased the wet soil aggregate stability and decreased the available Cu and Cd. The distribution of available heavy metals in wet soil aggregates was not controlled by soil aggregate stability, but possibly by soil organic carbon. PMID:26893180

Deep boreholes serve as natural laboratories for testing thermochronometers under geological conditions. The Kontinentale Tiefbohrung (KTB) is an interesting candidate because the geological evidence suggests that approximate isothermal holding since the last documented exhumation in the Late Cretaceous to Palaeocene is a reasonable assumption for the thermal histories of the KTB samples. We report 30 new apatite fission-track ages and 50 new mean confined track lengths determined on cores from the 4 km deep pilot hole. The ϕ- and ζ-external detector ages are consistent with the population ages from earlier studies and together define a clear age profile. The mean track lengths from this and earlier studies reveal the effects of experimental factors. The measured age and length profiles are compared with the predictions of 24 annealing models for isothermal holding. There are clear discrepancies between the measured and calculated profiles. Down to 1.5 km depth, the measured mean track lengths are shorter than the predicted. The balance of methodological evidence indicates that this is due to seasoning, i.e., a shortening of the fossil confined tracks without attendant age reduction. From 2.5 to 4.0 km depth, the mean track lengths are longer than the predictions. This suggests that the bias model that weights the probabilities of observing tracks of different length and which is based on experiments relating surface track densities to mean track lengths is not appropriate for confined tracks. Experimental and methodological factors are sometimes difficult to disentangle, but present a sufficient margin for there to be no need to go against the independent geological evidence. Unknown geological events cannot be ruled out but their existence cannot be inferred from the fission-track data alone, much less can the nature or magnitude of such events be specified.

Phosphoproteins can induce and stabilize calcium carbonate (CaCO3) vaterite, which has desirable features for high reactivity. The purpose of this study was to synthesize bioactive CaCO3 microspheres for bone regeneration. Sodium caseinate (NaCas)-containing CaCO3 microspheres, with the crystal phase of vaterite, were synthesized by fast precipitation in an aqueous solution of CaCl2, Na2CO3, and 2 mg/mL of NaCas. The uniform microspheres exhibited rougher surfaces and lower negative charges than CaCO3 particles without NaCas addition. Fourier-transform infrared spectroscopy (FT-IR) of the microspheres showed characteristic peaks or bands corresponding to phosphate and hydroxyl groups. Thermogravimetric analysis (TGA) curves exhibited approximately 5% weight loss below 600 °C due to the decomposition of NaCas. Scanning electron microscope (SEM) images showed lath-like hydroxyapatite (HAp) on the surface after soaking in simulated body fluid (SBF) at 37 °C for 5 and 10 days. Energy dispersive X-ray spectrometry (EDS) revealed that the agglomerates were composed of Ca, C, O, P, Na, and Mg elements, and the Ca/P ratios ranged from 1.53 to 1.56. X-ray diffraction (XRD) patterns exhibited peaks characteristic of hydroxyapatite. The results of this study demonstrated that the addition of NaCas induced the formation of vaterite microspheres which possesses an enhanced apatite formation after soaking in SBF at 37 °C for 5 and 10 days. These NaCas-CaCO3 microspheres may be a potential biomaterial for bone regeneration.

The Taranaki basin, which extends offshore between the north and south island of New Zealand, contains several large gas fields (e.g., Maui field) and smaller oil fields. The Taranaki basin is New Zealand's only productive hydrocarbon basin. The basin trends north-south, is asymmetrical in cross section, and is faulted with up to 7 km of displacement along parts of its eastern margin. Preliminary results from Apatite Fission Track Analysis (AFTA) reveal the timing and magnitude of basin inversion. Four well cross sections from the southern part of the basin have been used. Initially, basin tectonics and sedimentation were associated with extension and the formation of half-grabens that began in the Late Cretaceous with the breakup of Gondwana. However, most of the observed subsidence and sedimentation resulted from mid-Cenozoic rifting throughout western New Zealand. Following the formation of the modern Australia-Pacific plate boundary during the early Miocene, the southern part of the basin, which lies 60 km from the Alpine fault in places, was partially inverted. AFTA parameters (apparent age and length) downhold at the Fresne-1 well show a distinct break in slope at 1,100 m depth (currently at 30/sup 0/C) where the apparent age is 15 Ma for the Late Cretaceous Parkawau Coal Measures. The data indicate that basin inversion began about 15 Ma and was accompanied by the removal of 2-3 km of section. Sedimentation began again in the Taranaki basin during the mid-Pliocene. The source of the gas and gas condensate in the basin is probably the Eocene coal measures. The maturation history of these beds and the overlying reservoirs was modeled using the constraints from AFTA data. Discrepancies exist between estimates of maximum paleotemperature from AFTA results and from vitrinite reflectance.

Titanium as one kind of biomaterials comes in direct contact with the body, making evaluation of biocompatibility an important aspect to biomaterials development. Surface chemistry of titanium plays an important role in osseointegration. Different surface modification alters the surface chemistry and result in different biological response. In this study, three kinds of mixed acid solutions were used to treat Ti specimens to induce Ca-P formation. Following a strong mixed acid activation process, Ca-P coating successfully formed on the Ti surfaces in simulated body fluid. Strong mixed acid increased the roughness of the metal surface, because the porous and rough surface allows better adhesion between Ca-P coatings and substrates. After modification of titanium surface by mixed acidic solution and subsequently H2O2/HCL treatment evaluation of biocompatibility was conducted from hydroxyapatite formation by biomimetic process and cell viability on modified titanium surface. Nano-scale modification of titanium surfaces can alter cellular and tissue responses, which may benefit osseointegration and dental implant therapy. Results from this study indicated that surface treatment methods affect the surface morphology, type of TiO2 layer formed and subsequent apatite deposition and biological responses. The thermo scientific alamarblue cell viability assay reagent is used to quantitatively measure the viability of mammalian cell lines, bacteria and fungi by incorporating a rapid, sensitive and reliable fluorometric/colorimetric growth indicator, without any toxic and side effect to cell line. In addition, mixed acid treatment uses a lower temperature and shorter time period than widely used alkali treatment. PMID:27433617

The sintering of silicon doped calcium phosphate ceramics prepared from a basic colloidal hydroxyapatite (Ca5(PO4)3OH or HA) precipitate mixed with silica over 800 degrees C yields a phase mixture of tricalcium phosphate phases (TCP) designated Si-TCP, beta-TCP and a silicon substituted dehydrated apatite (Si-Ap). The Si-TCP phase is defined as a combination of a silicon stabilized TCP in which the silicon content attains a saturated value (Ca3(P0.9Si0.1O3.95)2 or Si-TCP(sat)) and alpha-TCP (Ca3(PO4)2). Si-TCP(sat) has the same crystalline space group (P2(1)/a) as alpha-TCP, but with characteristically different lattice parameters due to the substitution of silicon in tetrahedral phosphorus sites. The nucleation and growth kinetics of Si-TCP in samples of composition 0.2 mol SiO2:mol HA (0.2:1) and 1 mol SiO2:mol HA (1:1) can be understood in terms of the initial growth of alpha-TCP at a silica-HA interface followed by a transformation to Si-TCP(sat) or beta-TCP. A thermodynamic model for the formation of Si-TCP(sat) predicts a nucleation temperature of 795 degrees C, in close agreement with experiment. If sufficient silicon is available, the alpha-TCP transforms to Si-TCP(sat) during extended sintering. In the absence of sufficient silicon, the alpha-TCP transforms to beta-TCP. PMID:15603784

The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems. The aim of this study was to quantify, for the first time, the dissolution rate of apatite grains by tree roots that were or were not associated with a mineral weathering bacterial strain, and by various acids known to be produced by tree roots and soil bacterial strains in open-system flow microcosms. In addition, we explored whether the mobilization of trace elements (including rare earth elements) upon apatite dissolution was affected by the presence of trees and associated microorganisms. The dissolution rate of apatite by Scots pine plants that were or were not inoculated with the strain Burkholderia glathei PML1(12)Rp, and by inorganic (nitric) and organic (citric, oxalic and gluconic) acids at pH 5.5, 4.8, 3.8, 3.5, 3.0, and 2.0 was monitored in two controlled experiments: "plant-bacteria interaction" and "inorganic and organic acids". Analyses of the outlet solutions in the "plant-bacteria interaction" experiment showed that Scots pine roots and B. glathei PML1(12)Rp produced protons and organic acids such as gluconate, oxalate, acetate, and lactate. The weathering budget calculation revealed that Scots pines (with or without PML1(12)Rp) significantly increased (factor > 10) the release of Ca, P, As, Sr, Zn, U, Y, and rare earth elements such as Ce, La, Nd from apatite, compared to control abiotic treatment. Scanning electron microscopy observation confirmed traces of apatite dissolution in contact of roots. Most dissolved elements were taken up by Scots pine roots, i.e., approximately 50% of Ca, 70% of P, 30% of As, 70% of Sr, 90% of Zn, and 100% of U, Y, and rare earth elements. Interestingly, no significant additional effect due to the bacterial strain PML1(12)Rp on apatite dissolution and Scots pine nutrition and growth was observed. The "inorganic

The abundances of trace elements including Sr, Ga and rare earth elements (REE) and halogens in apatite crystals from four intermediate-felsic plutons in the Zhongdian terrane in the Sanjiang region have been determined using electron microprobe and laser ablation inductively coupled plasma mass spectrometry to evaluate the potential of apatite as a petrogenic-metallogenic indicator. The selected plutons include one that is not mineralized (the Triassic Xiuwacu pluton, or the TXWC pluton), one that hosts a porphyry-type Cu deposit (the Pulang pluton, or the PL pluton), one that hosts a porphyry-type Mo deposit (the Tongchanggou pluton, or the TCG pluton), and one that hosts a vein-type Mo deposit (the Cretaceous Xiuwacu pluton, or the CXWC pluton). Except for the CXWC pluton, the other three plutons have adakite-like trace element signatures in whole rocks. The results from this study show that REE, Sr and halogens in apatite can be used to track magma compositions, oxidation states and crystallization history. Apatite crystals from the adakite-like plutons are characterized by much higher Sr/Y and δEu than the non-adakite-type pluton. This means that apatite, which is not susceptible to alteration, is a useful tool for identifying the adakite-like plutons that no longer preserve the initial Sr/Y ratios in whole rocks due to weathering and hydrothermal alteration. Based on apatite Ga contents and δEu values, it is inferred that the parental magmas for the two adakite-like plutons containing porphyry-type Cu and Mo mineralization are more oxidized than that for the non-adakite-type pluton containing vein-type Mo mineralization. Apatite crystals from the vein-type Mo deposit have much lower Cl/F ratios than those from the porphyry-type Cu and Mo deposits. Apatite crystals from the adakite-like pluton without Cu or Mo mineralization is characterized by much lower Cl/F ratios than those from the adakite-like plutons that host the porphyry-type Cu and Mo deposits. The

In order to provide a time constraint on the 13C-depleted kerogen in silica dikes that intruded 3.5 Ga greenstone from Pilbara Craton in Western Australia, we have carried out an ion microprobe U-Pb dating and rare earth element (REE) analysis of apatite from the dike. Two types of apatite were identified in the dikes based on their occurrences. One is stick-shape apatites (Type 1) in secondary silica micro-veins that cut the silica dike. The other is granular apatites (Type 2) that occurs in matrix of the dike. Occurrence in the secondary micro-veins (Type 1), non-igenous chondrite normalized REE patterns (Type 1 and 2), chemical zoning (some of Type 1 and 2), and presence of mineral inclusion that is composed of Fe and S (some of Type 2) suggest that both Type 1 and 2 apatites were crystallized in the silica dike. Ion microprobe U-Pb dating of Type 1 apatite did not give a meaningful age, while Type 2 apatite yields a Tera-Wasserburg concordia intercept age of 3214 +/- 140 Ma (95 per cent confidence level, MSWD = 0.6) in a three-dimensional 238U/206Pb-207Pb/206Pb-204Pb/206Pb diagram, and a 204Pb/206Pb-207Pb/206Pb isochron age of 3191 +/- 150 Ma (95 per cent confidence level, MSWD = 0.5). It is difficult to judge whether the U-Pb and Pb-Pb age of Type 2 apatite is crystallization age or metamorphic age, since the estimated range of closure temperature of U-Pb system in the apatite and that of metamorphic temperature is partly overlapped. In either case, it can be safely concluded that the minimum age of the dike and kerogen is 3.0 Ga. These ages might allow the interpretation that the kerogen was produced by biological carbon fixation and/or abiological reaction (such as Fischer-Tropsch Type reaction) at least before 3.0 Ga.

Calcium phosphate (CaP) thin films with different degrees of crystallinity were coated on the surfaces of commercially pure titanium by electron beam evaporation. The details of apatite nucleation and growth on the coating layer were investigated in Dulbecco's phosphate-buffered saline solutions containing calcium chloride (DPBS) or DPBS with fibronectin (DPBSF). The surfaces of the samples were examined by field emission scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The concentrations of fibronectin and calcium ions (Ca(2+)) were monitored by the bicinchoninic acid method (BCA) and use of a calcium assay kit (DICA-500), respectively. Apatite initially formed at the fastest rate on the CaP-coated samples with the lowest degree of crystallinity and reached the maximum Ca(2+) concentration after immersion in DPBS solution for 15min. After 15min the concentration of Ca(2+) decreased with the growth of apatite on the coating layers. For all the samples the maximum Ca(2+) concentration in the DPBS solutions decreased with increasing crystallinity and immersion time to reach the maximum concentration increased. The presence of fibronectin in the DPBS solutions delayed the formation and affected the morphology of the apatite. Fibronectin incorporated into apatite deposited on the surface of titanium did not affect its biological activity in terms of promoting osteoblast adhesion. PMID:19962459

In order to shed some light on DNA preservation over time in skeletal remains from a physicochemical viewpoint, adsorption and desorption of DNA on a well characterized synthetic apatite mimicking bone and dentin biominerals were studied. Batch adsorption experiments have been carried out to determine the effect of contact time (kinetics), DNA concentration (isotherms) and environmentally relevant factors such as temperature, ionic strength and pH on the adsorption behavior. The analogy of the nanocrystalline carbonated apatite used in this work with biological apatite was first demonstrated by XRD, FTIR, and chemical analyses. Then, DNA adsorption kinetics was fitted with the pseudo-first order, pseudo-second order, Elovich, Ritchie and double exponential models. The best results were achieved with the Elovich kinetic model. The adsorption isotherms of partially sheared calf thymus DNA conformed satisfactorily to Temkin's equation which is often used to describe heterogeneous adsorption behavior involving polyelectrolytes. For the first time, the irreversibility of DNA adsorption toward dilution and significant phosphate-promoted DNA desorption were evidenced, suggesting that a concomitant ion exchange process between phosphate anionic groups of DNA backbone and labile non-apatitic hydrogenphosphate ions potentially released from the hydrated layer of apatite crystals. This work should prove helpful for a better understanding of diagenetic processes related to DNA preservation in calcified tissues.

We propose to develop an infiltration strategy that defines the precipitation rate of an apatite-forming solution and Sr-90 sequestration processes under variably saturated (low water content) conditions. We will develop this understanding through small-scale column studies, intermediate-scale two-dimensional (2-D) experiments, and numerical modeling to quantify individual and coupled processes associated with apatite formation and Sr-90 transport during and after infiltration of the Ca-citrate-PO4 solution. Development of capabilities to simulate these coupled biogeochemical processes during both injection and infiltration will be used to determine the most cost-effective means to emplace an in situ apatite barrier with a longevity of 300 years to permanently sequester Sr-90 until it decays. Biogeochemical processes that will be investigated are citrate biodegradation and apatite precipitation rates at varying water contents as a function of water content. Coupled processes that will be investigated include the influence of apatite precipitation (which occupies pore space) on the hydraulic and transport properties of the porous media during infiltration.

The surface properties of biomaterials determine the interactions between biomedical devices and the surrounding biological environment. The surface modification of biomaterials is extensively recognized as a key strategy in the design of the next generation of bone implants and tissue engineering. In this study, the highly ordered octacalcium phosphate (OCP) coating and OCP/protein coating with hierarchically porous structure in nano-micro scale were constructed on titanium substrate by electrochemically-induced deposition (ED). The formation behavior of apatite on OCP and OCP/protein coatings immersed in simulated body fluid (SBF) was investigated in physicochemical aspects. It is indicated that soaked in SBF, the OCP and OCP/protein coatings are possible to induce relevant apatite formation on their surface, and the apatite-forming behavior in body environment is depended on the chemical composition and structure of the coatings. The apatite formed on OCP/protein composite coating possesses carbonated structure, needle-like crystals in nano scale, lower Ca/P ratio and higher degree of the preferred c-axis orientation, which are similar to the mineral composition and structure in natural bone, and hence called as bone-like apatite.

Apatite-type Lanthanum silicate (LSO) is among the most promising electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs) owing to the high conductivity and low activation energy at lower temperature than traditional doped-zirconia electrolyte. The ionic conductivity as well as the sintering density of lanthanum silicate oxy-apatite, La10Si6-xCuxO27-δ (LSCO, 0 ≤ x ≤ 2), was effectively enhanced through a small amount of doped copper. The phase composition, relative density, ionic conductivity and thermal expansion behavior of La10Si6-xCuxO27-δ was systematically investigated by X-ray diffraction (XRD), Archimedes' drainage method, scanning electron microscope (SEM), electrochemical impedance spectra (EIS) and thermal dilatometer techniques. With increasing copper doping content, the ionic conductivity of La10Si6-xCuxO27-δincreased, reaching a maximum of 4.8 × 10-2 S cm-1 at 800 °C for x = 1.5. The improved ionic conductivity could be primarily associated with the enhanced grain conductivity. The power output performance of NiO-LSCO/LSCO/LSCF single cell was superior to that obtained on NiO-LSO/LSO/LSCF at different temperatures using hydrogen as fuel and oxygen as oxidant, which could be attributed to the enhanced oxygen ionic conductivity as well as the sintering density for the copped doped lanthanum silicate. In conclusion, the apatite La10Si4.5Cu1.5O25.5 is a promising candidate electrolyte for IT-SOFCs.

The substitution of rare-earth elements (REEs) for Pb in the lacunary apatite Pb8Na2(PO4)6 with void structural channels was studied by means of powder X-ray diffraction (including the Rietveld refinement), scanning electron microscopy, energy-dispersive X-ray microanalysis, and IR spectroscopy and also measurements of the electrical conductivity. The substitution limits (xmax in Pb8-xLnxNa2(PO4)6Ox/2) at 800 °C were found to decrease with the atomic number of the REE from 1.40 for La to 0.12 for Yb with a rapid drop from light to heavy lanthanides (between Gd and Tb). The REE atoms substitute for Pb predominantly at Pb2 sites of the apatite structure according to the scheme 2Pb(2+) + □ → 2Ln(3+) + O(2-), where □ is a vacancy in the structural channel. The substitution in lacunary apatite produces quite different changes in the structural parameters compared with broadly studied alkaline-earth hydroxyapatites. In spite of the much lower ionic radii of REE than that of Pb(2+), the mean distances ⟨Pb1-O⟩ somewhat increase, whereas the distances ⟨Pb2-Pb2⟩ and ⟨Pb2-O4⟩ do not change considerably with the degree of substitution. This implies control of the substitution by not only spatial and charge accommodation of REE ions but also the availability of a stereochemically active 6s(2) electron pair on Pb(2+). The high-temperature electrical conductivity shows dependence on the degree of substitution with a minimum at x = 0.2 indicative of a possible change of the type of conductivity. PMID:26871754

Apatite fission track ages indicates that a large component of motion along many of the present range-bounding faults occurred in the Early to Middle Miocene, tilting and uplifting rocks through the apatite annealing zone (120--60 C) between 18--13 Ma (n = 20, Deep Creeks), 18--15 Ma (northern Snake Range, n = 20), 25--17 Ma (n = 7, southern Snake Range), 24--15 Ma (Egan Range, n = 6), 23--18 Ma (Kern Mts., n = 2) and 28--16 ma (Schell Creek Range, n = 2). Long track length distributions indicate rapid cooling through the 120--60 C interval followed by residence at low, near surface temperatures. The data set also indicates that the combined Deep Creek-Kern Mountains-northern and southern Snake Range constitutes a single coherent footwall crustal block beneath a > 150 km-long system of east-dipping Miocene faults which includes at least the eastern portions of faults that have been mapped as the Snake Range decollement (NSRD). Conglomerates deposited in hanging wall basins along this fault system contain metamorphic and granitic boulders whose FT ages are coeval with footwall unroofing. The deposits themselves are now known to be younger than previously reported (Oligocene) as ages from boulders are Miocene. The thick (> 2 km) sequences of synorogenic conglomerate indicates rapid unroofing; large slide blocks attest to generation of steep, fault-controlled topography. Faults that cut this sequence are now known to be younger than 15 Ma. Thus, protracted extensional faulting affected the region, beginning in the Early Oligocene and continuing to the Recent, but a significant part of this extension, including a large component of the slip on the NSRD, was accomplished in the Early to Middle Miocene. Data from this region is compatible with a growing base of apatite fission track data from elsewhere in the northern Basin and Range, which, together with geologic relationships, suggest an important episode of Miocene extension and Basin and Range development.

Some dental ceramics were coated with a bioactive glass and resulted the formation of a stable and well bonded with the ceramic substrate thin layer. After immersion in a solution with ion concentrations similar to those of human blood plasma the development of hydroxy carbonate apatite layer on the surface of bioactive glass may be observed. The objective of this study was to investigate structural surface changes of bioactive glass, after exposure in a simulated body fluid for a different number of days. The roughness and topography of the hydroxyapatite surface were investigated by Confocal Scanning Laser Microscopy. The chemical composition was analyzed by Energy Dispersive Spectroscopy measurements.

The Cretaceous Ningwu volcanic basin of the Middle and Lower Yangtze River Valley metallogenic belt of eastern China hosts numerous Fe-oxide-apatite, Cu-Au, and pyrite deposits. The mineralization in the Ningwu basin is associated with subvolcanic rocks, consisting of gabbro-diorite porphyry and/or pyroxene diorite. However, the mineralization is associated with subvolcanic and volcanic rock suite belonging to the Niangniangshan Formation in the Tongjing Cu-Au deposit, including nosean-bearing aegirine-augite syenites, quartz syenites, and quartz monzonites. The zoning displayed by the alteration and mineralization comprises: (1) an upper light-colored zone of argillic, carbonate, and pyrite alteration and silicification that is locally associated with pyrite and gold mineralization, (2) a central dark-colored zone of diopside, fluorapatite-magnetite, phlogopite, and garnet alteration associated with fluorapatite-magnetite mineralization, and (3) a lowermost light-colored zone of extensive albite alteration. The Cu-Au and pyrite orebodies are peripheral to the Fe-oxide-apatite deposits in this area and overlie the iron orebodies, including the Meishan Cu-Au deposit in the northern Ningwu basin and the pyrite deposits in the central Ningwu basin. The δ34S values of sulfides from the Fe-oxide-apatite, Cu-Au, and pyrite deposits in the Ningwu basin show large variation, with a mixed sulfur source, including magmatic sulfur and/or a mixture of sulfur derived from a magmatic component, country rock, and thermochemical reduction of sulfate at 200-300 °C. The ore-forming fluids associated with iron mineralization were derived mainly from magmatic fluids, and the late-stage ore-forming fluids related to Cu-Au and pyrite mineralization may have formed by the introduction of cooler meteoric water to the system. The Fe-oxide-apatite, Cu-Au, and pyrite deposits of the Ningwu basin formed in an extensional environment and are associated with a large-scale magmatic

Analyses were made of uranium and thorium in ziircon, sphene, apatite, epidote, and monazite separated as accessory minerals from samples of granitic rock from widely scattered localities to indicate the abundance and distribution of these two elements among the five mineral phases. For any pair of mineral phases the distribution ratio remains within the same order of magnitude over the different rocks tested, although the variability of the data is such that only wide departures from constancy could be ascertained. Such gross differences have not been found.

Using calcium phosphate glass targets with the CaO/P2O5 molar ratios of 1.50-0.50, much lower than the stoichiometric value of 3.3 for hydroxyapatite, thin films of stoichiometric hydroxy-, nonstoichiometric oxyhydroxy- and Ca-deficient oxyhydroxy-apatites were prepared on alumina ceramic substrates by rf-sputtering followed by post-annealing. Based on the present results, a phase diagram for CaO-P2O5 at low temperatures in the ambience of air was depicted for thin films. The ambient H2O vapor had an influence on the phase diagram: Tricalcium phosphate was changed to apatite in the presence of H2O vapor. Dense fluorohydroxyapatite thin films were prepared by fluoridation of those apatite thin films at a low temperature such as 200 degrees C. In the present report, some functional properties of thin films thus prepared were also shown. PMID:9720887

The Sierra de Chiapas (SCH), located in the south of Mexico, is a complex geological province that can be divided on four different lithological or tectonic areas: (1) the Chiapas Massif Complex (CMC); (2) the Central Depression; (3) the Strike-slip Fault Province, and (4) the Chiapas Fold-and-thrust Belt. The CMC mostly consists of Permian granitoids and meta-granitoids, and represents the basement of the SCH. During the Jurassic period red beds and salt were deposited on this territory, related to the main pulse of rifting and opening of the Gulf of Mexico. Most of the Cretaceous stratigraphy contains limestones and dolomites deposited on a marine platform setting during the postrift stage of the Gulf of Mexico rift. During the Cenozoic Era took place the major clastic sedimentation along the SCH. According the published low-temperature geochronology data (Witt et al., 2012), SCH has three main phases of thermo-tectonic history: (1) slow exhumation between 35 and 25 Ma, that affected mainly the basement (CMC) and is probably related to the migration of the Chortís block; (2) fast exhumation during the Middle-Late Miocene caused by strike-slip deformation that affects almost all Chiapas territory; (3) period of rapid cooling from 6 to 5 Ma, that affects the Chiapas Fold-and-thrust Belt, coincident with the landward migration of the Caribbean-North America plate boundaries. The two last events were the most significant on the formation of the present-day topography of the SCH. However, the stratigraphy of the SCH shows traces of the existence of earlier tectonic events. This study presents preliminary results of apatite fission-track (AFT) dating of sandstones from the Todos Santos Formation (Middle Jurassic). The analyses are performed with in situ uranium determination using LA-ICP-MS (e.g., Hasebe et al., 2004). The AFT data indicate that this Formation has suffered high-grade diagenesis (probably over 150 ºC) and the obtained cooling ages, about 70-60 Ma

change and the associated change in moisture content so that 4D images of moisture content change can be generated. Results from this field test will be available for any future Ca-citrate-PO4 amendment infiltration tests, which would be designed to evaluate the efficacy of using near surface application of amendments to form apatite mineral phases in the upper portion of the zone of water table fluctuation.

The Malmberget mine is the World's second largest underground iron ore operation. It is composed of approximately 20 apatite iron ore bodies, whereas 13 ore bodies with 5-245 Mt each are presently mined. The massive magnetite ore is hosted within volcanic and volcaniclastic rocks. Host rocks within the entire area were subject to intense hydrothermal alteration. The ore reserves at beginning of 2012 totalled 290 Mt at 44 percent iron. Together with Kiruna and Svappavaara these three deposits stands for more than 90 percent of the iron ore production in Europe. An on-going collaborative research project aims at unravelling the structural geometries, relationships and control on ore formation and ore body transposition at different scales in the Gällivare district in general and in the Malmberget mine in particular. Recent results show the three-dimensional crustal architecture of the Malmberget deposit which has undergone at least two separate deformation events. The first deformation event (D1) resulted in the formation of a strong and penetrative cleavage (S1) forming a varyingly intense banding within the volcanic rocks. The D1-event coincides with the amphibolite facies peak metamorphism in the area. Distinct, biotite-rich D1 shear zones are spatially related to the majority of the S1-parallel massive magnetite bodies. These D1 shear zones seem to be responsible for a strong strain partitioning during D1. A second compressional event (D2) resulted in open to close folding of the S1 fabric, the D1 shear zones and the related ore bodies. The result is an asymmetric F2-synform with moderately south-west-plunging fold axis. Furthermore, distinct D2 high strain zones are responsible for local transposition of S1 fabrics, tight to isoclinal folding and channeling or re-mobilization of hydrothermal alteration minerals. Both deformation events are accompanied by syn- and late-tectonic granitic intrusions forming both foliated and unfoliated and commonly boudinaged

Recent work indicates that He diffusion from apatite is impeded by the accumulation of radiation damage from actinide decay. Supporting evidence includes laboratory diffusion measurements as well as (U-Th)/He dates positively correlated with effective uranium (eU) concentration in certain geologic situations. Here we investigate whether the radiation damage effect can be identified in 4He concentration profiles, as it must be if the system behaves as we anticipate. Apatites from nearby igneous basement samples in the Upper Gorge of the Grand Canyon showing a strong date-eU correlation were proton irradiated, step-heated, and analyzed for 4He/3He spectra. The low eU apatites with younger He dates yielded nearly flat spectra, while the high eU apatites with older He dates yielded highly rounded spectra (see Figure). This implies that the higher eU apatites were partially retaining He while the lower eU apatites were still acting as an open system. Using the RDAAM kinetic model (Flowers et al. 2009) and local geologic constraints we confirm that this behavior is consistent with the observed differences in date and eU, providing compelling evidence that both the He dates and the 4He profiles are sensitive to radiation damage accumulation. Equally importantly, the combination of multiple samples with differing eU and thus differing 4He/3He spectra yields remarkably tight constraints on the time-temperature path experienced by these rocks, from ~90oC down to < 30oC.

The Ibar Basin was formed during Miocene large scale extension in the NE Dinaride segment of the Alpine- Carpathian-Dinaride system. The Miocene extension led to exhumation of deep seated core-complexes (e.g. Studenica and Kopaonik core-complex) as well as to the formation of extensional basins in the hanging wall (Ibar Basin). Sediments of the Ibar Basin were studied by apatite and zircon fission track and vitrinite reflectance in order to define thermal events during basin evolution. Vitrinite reflectance (VR) data (0.63-0.90 %Rr) indicate a bituminous stage for the organic matter that experienced maximal temperatures of around 120-130 °C. Zircon fission track (ZFT) ages indicate provenance ages. The apatite fission track (AFT) single grain ages (45-6.7 Ma) and bimodal track lengths distribution indicate partial annealing of the detrital apatites. Both vitrinite reflectance and apatite fission track data of the studied sediments imply post-depositional thermal overprint in the Ibar Basin. Thermal history models of the detritial apatites reveal a heating episode prior to cooling that began at around 10 Ma. The heating episode started around 17 Ma and lasted 10-8 Ma reaching the maximum temperatures between 100-130 °C. We correlate this event with the domal uplift of the Studenica and Kopaonik cores where heat was transferred from the rising warm footwall to the adjacent colder hanging wall. The cooling episode is related to basin inversion and erosion. The apatite fission track data indicate local thermal perturbations, detected in the SE part of the Ibar basin (Piskanja deposit) with the time frame ~7.1 Ma, which may correspond to the youngest volcanic phase in the region.

Calcium phosphate cements (CPCs) can be considered as good candidate for bone tissue engineering because they can be resorbed and take part in the bone remodeling process. Several efforts have been made into improve the resorption rate of the calcium phosphate cement by introducing macropores to the cement matrix. In this investigation a simple and effective method has been presented based on the addition of various amounts of an effervescent agent to the calcium phosphate cement components. The effervescent agent was a mixture of sodium hydrogen carbonate, NaHCO(3) (that was added to the powder phase), and citric acid monohydrate, C(6)H(8)O(7).H(2)O (that was dissolved in the liquid phase). The obtained macroporous samples were characterized by Fourier transform infrared spectrometer, X-ray diffraction, and scanning electron microscopy techniques at 4 h after setting and 3 days after soaking in a special simulated body fluid solution named Hank's balanced salt solution. Mercury intrusion porosimetry was also employed for characterizing the pore volume and pore size distribution in the cement structure. Results showed that the rate of conversion of staring reactant to the apatite phase and the apatite chemistry were significantly changed by using the additive in the cement components. Also both the pore volume and pore size were changed by varying both the amount of effervescent additive and the powder to liquid ratio. PMID:17380498

Research on synthetic bioactive bone graft materials has significantly expanded in the past decade. In this study, the nanocomposite scaffold of semi-interpenetrating networks (semi-IPN) cellulose-graft-polyacrylamide/nano-hydroxyapatite was synthesized through free radical polymerization. The scaffolds were fabricated by the freeze-drying technique. The prepared semi-IPN nanocomposite scaffolds were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) analysis. In addition, the mechanical properties (i.e., elastic modulus and compressive strength) of the scaffolds were investigated. The SEM images showed that the pores of the scaffolds were interconnected, and their sizes ranged from 120μm to 190μm. Under optimum conditions, the prepared scaffolds had a compressive strength of 4.80MPa, an elastic modulus of 0.29GPa and a value of 47.37% porosity. Furthermore, the apatite-forming ability of the scaffolds was determined using simulated body fluid (SBF) for 28 days. The results revealed that the new apatite particles could grow on the surface of the scaffolds after a 14-day immersion in SBF. Finally, this study suggests that the prepared semi-IPN nanocomposites that closely mimic the properties of bone tissue could be a promising scaffold for bone tissue engineering. PMID:26836617

The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U–Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U–Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years. PMID:24349912

Apatite fission track and vitrinite reflectance are integrated for the first time to study the cooling history in the Central Tarim, northwest China. The paleo-temperature profiles from vitrinite reflectance data of the Z1 and Z11 wells showed a linear relationship with depth, suggesting an approximately 24.8 °C/km paleo-geothermal gradient and 2700-3900 m of erosion during the Early Mesozoic. The measured apatite fission track ages from well Z2 in the Central Tarim range from 39 to 159 Ma and effectively record the Meso-Cenozoic cooling events that occurred in Central Tarim. Moreover, two cooling events at 190-140 Ma in the Early Jurassic-Early Cretaceous and 80-45 Ma in the Late Cretaceous-Paleocene revealed by measured AFT data and thermal modeling results are related to the collisions of the Qiangtang-Lhasa terranes and the Greater India Plate with the southern margin of the Eurasian Plate, respectively. This study provides new insights into the tectonic evolution of the Tarim Basin (and more broadly Central Asia) and for hydrocarbon generation and exploration in the Central Tarim.

ability to constrain km-scale exhumation with apatite 4He/3He thermochronometry is well established and the technique has been applied to a range of tectonic and geomorphic problems. However, multiple sources of uncertainty in specific crystal characteristics limit the applicability of the method, especially when geologic problems require identifying small perturbations in a cooling path. Here we present new 4He/3He thermochronometric data from the Appalachian Mountains, which indicate significant parent nuclide zonation in an apatite crystal. Using LA-ICPMS measurements of U and Th in the same crystal, we design a 3-D model of the crystal to explore the effects of intracrystal variability in radiation damage accumulation. We describe a numerical approach to solve the 3-D production-diffusion equation. Using our numerical model and a previously determined time temperature path for this part of the Appalachians, we find excellent agreement between predicted and observed 4He/3He spectra. Our results confirm this time-temperature path and highlight that for complex U and Th zonation patterns, 3-D numerical models are required to infer an accurate time-temperature history. In addition, our results provide independent and novel evidence for a radiation damage control on diffusivity. The ability to exploit intracrystal differences in 4He diffusivity [i.e., temperature sensitivity) greatly increases the potential to infer complex thermal histories.

The present study reports the variations in phase content of biphasic mixtures and structural changes induced by different levels of strontium addition in calcium-deficient apatite (Ca/P = 1.60) powders during heat treatment. The synthesis was attempted by an in situ aqueous precipitation technique and X-ray diffraction, Raman spectroscopy and Rietveld refinement of the powder X-ray diffraction data were employed for comprehensive analysis. The results confirm the preferential occupancy of Sr(2+) at two different Ca(2+) sites of the hydroxyapatite [Ca10(PO4)6(OH)2, HAP] lattice, with the Ca(2+) (2) site accommodating more Sr(2+) than the Ca(2+) (1) site. Increasing Sr(2+) addition in calcium-deficient apatite has led to a decline in the phase content of β-tricalcium phosphate [β-Ca3(PO4)2, β-TCP] in biphasic mixtures of HAP and β-TCP. Sr(2+) addition exceeding the critical limit of a (Ca + Sr)/P > 1.75 molar ratio has resulted in the formation of CaO as an additional phase, and this justifies the lack of enough PO4(3-) ions to promote any kind of calcium phosphate precipitation. Sr(2+) accommodation in the lattice sites of HAP has induced an increase in the lattice parameters and has also led to the significant distortion of the PO4 tetrahedron and OH groups, confirmed by Raman and FT-IR spectroscopic techniques. PMID:25851342

The feasibility of using indirect selective laser sintering (SLS) to produce parts from glass-ceramic materials for bone replacement applications has been investigated. A castable glass based on the system SiO2 x Al2O3 x P2O5 x CaO x CaF2 that crystallizes to a glass-ceramic with apatite and mullite phases was produced, blended with an acrylic binder, and processed by SLS. Green parts with good structural integrity were produced using a wide range of processing conditions, allowing both monolayer and multilayer components to be constructed. Following SLS the parts were post-processed to remove the binder and to crystallize fully the material, evolving the apatite and mullite phases. The parts were heated to 1200 degrees C using a number of different time-temperature profiles, following which the processed material was analysed by differential thermal analysis, X-ray diffraction, and scanning electron microscopy, and tested for flexural strength. An increase in strength was achieved by infiltrating the brown parts with a resorbable phosphate glass, although this altered the crystal phases present in the material. PMID:16459446

Apatite fission track and vitrinite reflectance are integrated for the first time to study the cooling history in the Central Tarim, northwest China. The paleo-temperature profiles from vitrinite reflectance data of the Z1 and Z11 wells showed a linear relationship with depth, suggesting an approximately 24.8 °C/km paleo-geothermal gradient and 2700-3900 m of erosion during the Early Mesozoic. The measured apatite fission track ages from well Z2 in the Central Tarim range from 39 to 159 Ma and effectively record the Meso-Cenozoic cooling events that occurred in Central Tarim. Moreover, two cooling events at 190-140 Ma in the Early Jurassic-Early Cretaceous and 80-45 Ma in the Late Cretaceous-Paleocene revealed by measured AFT data and thermal modeling results are related to the collisions of the Qiangtang-Lhasa terranes and the Greater India Plate with the southern margin of the Eurasian Plate, respectively. This study provides new insights into the tectonic evolution of the Tarim Basin (and more broadly Central Asia) and for hydrocarbon generation and exploration in the Central Tarim.

We synthesized composites of Eu(3+)-doped calcium apatite (CaAp:Eu(3+)) nanoparticles and silica particles via two methods: (i) in situ synthesis of CaAp:Eu(3+) in the presence of silica particles and (ii) electrostatic adsorption of CaAp:Eu(3+) nanoparticles on silica particle surfaces. In both methods, submicrometer spherical silica particles were covered with CaAp:Eu(3+) nanoparticles without forming any impurity phases, as confirmed by X-ray diffractometry, Fourier-transform infrared spectroscopy, and scanning electron microscopy. In method i, part of the silica surface acted as a nucleation site for apatite crystals and silica particles were inhomogeneously covered with CaAp:Eu(3+) nanoparticles. In method ii, positively charged CaAp:Eu(3+) nanoparticles were homogeneously adsorbed on the negatively charged silica surface through electrostatic interactions. The bonds between the silica surface and CaAp:Eu(3+) nanoparticles are strong enough not to break under ultrasonic irradiation, irrespective of the synthetic method used. The composite particles showed red photoluminescence corresponding to 4f → 4f transitions of Eu(3+) under near-UV irradiation. Although the absorption coefficient of the forbidden 4f → 4f transitions of Eu(3+) was small, the red emission was detectable with a commercial fluorescence microscope because the CaAp:Eu(3+) nanoparticles accumulated on the silica particle surfaces. PMID:25616077

The incorporation of a bioactive glass in the structure of hybrid polymers used in dentistry for the construction of fixed prosthetic restorations could induce the expression of bioactivity, leading to the possibility of periodontal tissues reattachment. Hybrid polymer specimens and polymer specimens modified by bioactive glass were prepared and used as control for the surface morphology examination by Scanning Electron Microscopy with associated Dispersive Spectroscopy Analysis (SEM-EDS) and for surface characterization with Fourier Transform Infrared Spectroscopy (FTIR). Furthermore, hybrid polymer specimens modified by bioactive glass were immersed in simulated body fluid (SBF) at 37 °C for different time intervals and were examined by SEM-EDS and FTIR. After 4 days immersion time a dense and continuous apatite layer covered almost the entire modified surface of the specimens. The molar Ca/P ratio reached the value of 1.79. The apatite layer showed a thickness of 1?m and was attached to the substrate, while bioactive glass particles were still present in polymer mass.

Nanoparticle-covered electrodes have altered properties as compared to conventional electrodes with same chemical composition. The changes originate from the large surface area and enhanced conduction. To test the mineralization capacity of such materials, TiO2 nanoparticles were deposited on titanium and gold substrates. The electrochemical properties were investigated using cyclic voltammetry and impedance spectroscopy while the mineralization was tested by immersion in simulated body fluid. Two types of nucleation and growth behaviours were observed. For smooth nanoparticle surfaces, the initial nucleation is fast with the formation of few small nuclei of hydroxyapatite. With time, an amorphous 2D film develops with a Ca/P ratio close to 1.5. For the rougher surfaces, the nucleation is delayed but once it starts, thick layers are formed. Also the electronic properties of the oxides were shown to be important. Both density of states (DOS) in the bandgap of TiO2 and the active area were determined. The maximum in DOS was found to correlate with the donor density (Nd) and the active surface area. The results clearly show that a rough surface with high conductivity is beneficial for formation of thick apatite layers, while the nanoparticle covered electrodes show early nucleation but limited apatite formation. PMID:23737786

Placing accurate age constraints on young volcanic eruptions, particularly in populated areas such as New Mexico, is important for not only tectonic and climate studies, but also for geohazard analysis. A primary lack of zircon and apatite crystals in basaltic rocks leaves K/Ar and 40Ar/39Ar dating as the most favored methods, though extraneous Ar and low K contents can often reduce precision. Alternative techniques suggested in recent years include (U-Th)/He dating of U and Th rich inclusions in olivine phenocrysts and other phenocrysts (Min et al., 2006; Aciego et al., 2007), (U-Th)/He dating of zircon xenocrysts (Blondes et al., 2007), and (U-Th)/He dating of magnetite phenocrysts (Blackburn et al., 2007). Unfortunately, zircon xenocrysts are not very abundant in basalts, and not all basalts contain suitably sized olivine, magnetite, or other phenocrysts. Here, we present a new application of the (U-Th)/He method to dating young volcanic eruptions in an area where the emplacement of basalt flows has reset the (U-Th)/He systematics of zircons and apatites in intercalated baked sediments. The Taos Plateau volcanic field (TPVF) in New Mexico formed in Middle to Late Miocene time in association with extensional processes in the Rio Grande Rift. The voluminous (>200 km3) basalt flows of the TPVF have been carefully dated with 40Ar/39Ar (Appelt, 1998) and therefore provide a sound basis for comparison with the (U-Th)/He results. Two fluvial sand and gravel samples were collected from directly beneath the Upper member of the Servilleta Basalt (40Ar/39Ar age: 3.57 ± 0.19 Ma [2 S.E., n = 3]; Appelt, 1998) in the Rio Grande River Gorge just west of Taos. These two samples yielded a distinct population of single-crystal (U-Th)/He zircon and apatite ages of 3.54 ± 0.11 Ma [2 S.E., n = 4] and 3.44 ± 0.25 Ma [2 S.E., n = 2] respectively. Sixteen additional grains (6 zircons and 10 apatites) gave significantly older dates (~ 9 to 27 Ma). We interpret the older dates as

Fluids including aqueous or aqueous-carbonic vapor, aqueous liquid, and hydrosaline liquid, if present in magma, influence magmatic and volcanic processes, and the exsolution of fluids from magma sequesters and buffers volatile components from melt thus impacting the textural and chemical evolution of melts and phenocrysts. Establishing the timing of initial magmatic fluid saturation and monitoring changes in fluid chemistry through textural interpretations are often challenging because primary magmatic fluid inclusions are uncommon to most plutonic systems and are extremely rare in phenocrysts of eruptive magmas. Moreover, miarolitic cavities, often interpreted to be a priori evidence of fluid exsolution, are rarely observed in igneous systems. Geochemical tools used to resolve magmatic volatile histories include the analysis and interpretation of melt inclusion compositions and those of hydrous minerals including micas, amphiboles, and apatite. We have conducted more than 50 new hydrothermal experiments involving apatite+rhyodacite melt±fluids at 28, 50, 100, 200, and 400 MPa, and have combined these new data with published results for apatite-saturated melts at 200 MPa. This integrated body of data supports determination of a broadly applicable geochemical relationship that correlates the mole fractions of H2O and Cl in apatite with mole fractions of H2O and Cl in coexisting silicate melt as a function of pressure, temperature, and melt composition (for felsic to basaltic melts). The mathematical expression of this relationship is useful for a wide variety of applications: constraining H2O, Cl, and F concentrations in silicate melts and hence verifying concentrations of magmatic volatiles determined from silicate melt inclusions; establishing pressures or temperatures of apatite crystallization or last equilibration with melt ± fluids (if temperature and pressure, respectively, are constrained from other geothermobarometers); determining concentrations of

To investigate the impact of glacial erosion on landscape evolution during the Quaternary, problems may occur in choosing the best method, because many methods only reflect parts of the era. Erosion rate calculations based on cosmogenic nuclides only cover the Holocene and erosion rate calculations based on river load gauging reflect even shorter timescales (e.g. von Blanckenburg 2005). In this study we investigate the potential of thermochronological methods, especially apatite fission track dating (AFT) to quantify glacial erosion in the European Alps. The topography of the European Alps is strongly influenced by Quaternary glaciations, as it formed characteristic features like overdeepened and hanging valleys. The study area is located in the Central Alps of Switzerland, which is a high mountain area. At ~0.9 Ma glacial erosion has led to a considerable increase in valley incision rates in this area (Haeuselmann et al. 2007) and therefore it is ideally suited to study the glacial impact on landscape evolution. The advantage of using AFT dating, while studying changes in erosional processes, is that possibly arising nonsteady-state erosion will be recorded within the spatial distribution of thermochronological ages. In this study we applied AFT dating on both bedrock and sediments. The bedrock samples derive from different elevations to figure out whether or not spatial differences and elevation dependencies exist. Combined with already published data we have a relatively high sample density distributed throughout the whole study area. The detrital samples originate from stream sediments and from glacial deposits in the form of late glacial moraines and cave sediments from the last ~0.5 Ma in order to obtain possible lateral variations in erosion. The AFT ages of the bedrocks vary between ~4 Ma and ~9 Ma, resulting in an average long-term exhumation rate of ~0.5 km/Ma. Most of the ages range between 7 and 9 Ma, confirmed by prevailing ages of stream sediment

The Henry Mountains are one of several laccolith-cored ranges on the Colorado Plateau that clearly preserve contact and structural relationships between Oligocene intrusions and the thick (~2.5 km) late Paleozoic and Mesozoic sedimentary package, which locally upwarped to accommodate laccolith emplacement. Here, we use the Henrys not only to add to the understanding of the thermal and geomorphic evolution of the Colorado Plateau, but also as a laboratory to explore possible links between pluton emplacement, localized rock uplift and exhumation. Published hornblende 40Ar/39Ar ages indicate intrusion between 31 and 23 Ma. The range comprises five main peaks (Ellen, Pennell, Hillers, Ellsworth and Holmes), each cored by a central laccolith and satellite intrusions emplaced at varying stratigraphic levels throughout the range. Regional stratigraphic correlation suggests the Mt. Hillers laccolith, which intruded the Permain Cutler Group, was at the time of emplacement overlain by at least the entire ~2.5 km Permian-Cretaceous sedimentary package. On the south side of Mt. Hillers these country rocks dip vertically, folded against the side of the main laccolith body and ramped at least one kilometer above local baselevel for these units; this is the classic example of localized uplift as a primary accommodation mechanism for magma emplacement, and at such shallow depths this roof lifting was surely itself accommodated by surface uplift and probably erosion. Despite these intriguing uplift indicators, apatite (U-Th)/He (AHe) dates from a 600 m vertical profile in these country rock sandstones and interbedded porphyry sills are nearly all 10-14 Ma, significantly younger than the age of emplacement and localized uplift. These data are consistent with intrusion at depths at least as deep as the AHe partial retention zone (PRZ; >~50-70°C, >~2-3 km), which agrees with stratigraphic estimates of emplacement depth. Also consistent with these data is cooling and exhumation of

Iron oxide-apatite (IOA) and iron oxide-copper-gold deposits (IOCG) are important sources of their namesake metals and increasingly for rare earth metals in apatite. Studies of natural systems document that IOA and IOCG deposits are often spatially and temporally related with one another and coeval magmatism. However, a genetic model that accounts for observations of natural systems remains elusive, with few observational data able to distinguish among working hypotheses that invoke meteoric fluid, magmatic-hydrothermal fluid, and immiscible melts. Here, we use Fe and O isotope data and high-resolution trace element (e.g., Ti, V, Mn, Al) data of individual magnetite grains from the world-class Los Colorados (LC) IOA deposit in the Chilean Iron Belt to elucidate the origin of IOA and IOCG deposits. Values of d56Fe range from 0.08‰ to 0.26‰, which are within the global range of ~0.06‰ to 0.5‰ for magnetite formed at magmatic conditions. Values of δ18O for magnetite and actinolite are 2.04‰ and 6.08‰, respectively, consistent with magmatic values. Ti, V, Al, and Mn are enriched in magnetite cores and decrease systematically from core to rim. Plotting [Al + Mn] vs. [Ti + V] indicates that magnetite cores are consistent with magmatic and/or magmatic-hydrothermal (i.e., porphyry) magnetites. Decreasing Al, Mn, Ti, V is consistent with a cooling trend from porphyry to Kiruna to IOCG systems. The data from LC are consistent with the following new genetic model for IOA and IOCG systems: 1) magnetite cores crystallize from silicate melt; 2) these magnetite crystals are nucleation sites for aqueous fluid that exsolves and scavenges inter alia Fe, P, S, Cu, Au from silicate melt; 3) the magnetite-fluid suspension is less dense that the surrounding magma, allowing ascent; 4) as the suspension ascends, magnetite grows in equilibrium with the fluid and takes on a magmatic-hydrothermal character (i.e., lower Al, Mn, Ti, V); 5) during ascent, magnetite, apatite and

To better understand the driving mechanisms behind the transition from collision to escape in a convergent plate tectonic setting, multiple low-temperature thermochronometers were used from the Arabia-Anatolia collisional belt. Within the accreted terranes of the Anatolian plate, Late Cretaceous and Eocene metamorphic and intrusive rocks were targeted to track regional and/or local exhumation patterns that may have occurred since collision initiated ~35-20 Ma. Forty-eight samples were collected in a ~200 km wide swath from the main Arabia-Anatolia suture, along and across three major fault zones: the East Anatolian Fault Zone (EAFZ), the Sürgü Fault, and the Central Anatolian Fault Zone (CAFZ). We report here both Apatite (U-Th)He (AHe) and Apatite Fission Track (AFT) analyses performed on the same samples. (1) From the EAFZ, two ~1200 m high vertical transects were sampled north and south of the main fault strand within the low-grade metamorphic rocks of the Pütürge Massif. Although a majority of apatite grains had extremely low uranium contents preventing acquisition of meaningful AHe ages, results from the few uranium-rich samples indicate ages ranging from 14 to 9 Ma in the northern flank of the EAFZ while the southern flank recorded younger exhumation around 5-3 Ma suggesting differential vertical displacement along the fault since ~10 Ma. In contrast, Zircon (U-Th)He results from both sides of the fault show comparable ages around 25-18 Ma. (2) Exposed in the vicinity of the dextral Sürgü Fault, Eocene granitic bodies from the Berit Mountains were sampled within 5 km south of the fault and over 500 m elevation. AHe results yield ages between 27 and 14 Ma. (3) Along the Ecemiş segment of the CAFZ, the Late Cretaceous Niğde metamorphic complex and its deformed Paleocene-Eocene sedimentary cover show AFT and AHe ages confined between 20 and 15 Ma implying fast cooling and exhumation at this time. Further south, the Eocene Horoz pluton that intruded the

Potential losses related to large earthquakes on blind or previously unrecognized thrust faults is of significant concern to southern California, where numerous individual mountain ranges are underlain by active faults. Some of the most hazardous thrust fault systems in Southern California are associated with high-slip-rate faults in the northern portion of the western Transverse Ranges, while the southern region is generally considered to be less seismically active. Determining slip rates on faults bounding the Santa Monica Mountains has been challenging, in part because many of the faults that underlie the range have submarine surface traces. Existing geologic studies predict that these faults slip relatively slowly; however, recent GPS models predict a band of relatively fast contraction on faults that lie beneath the Santa Monica Mountains (Marshall et al., 2013). These geodetic models suggest unrecognized hazard associated with shortening and vertical uplift of this range. Late Cenozoic strata in the central Santa Monica Mountains are of sufficient thickness to bury Cretaceous and Paleocene strata above the closure temperature for apatite (U-Th)/He thermochronometry (~70°C). As a result, these older rocks, now exposed in the southern Santa Monica Mountains, may record exhumation associated with fault slip and associated structural deformation of the range. Preliminary apatite (U-Th)/He ages near Las Flores Canyon span from 3.5 to 6.5 Ma, and are the youngest apatite (U-Th)/He ages we are aware of in southern California outside of the transpressional San Andreas system. When plotted as depth beneath the base of the marine Modelo Formation, an inflection in age/depth gradient at 4 Ma is inferred to reflect the onset of fault motion and is consistent with the late Miocene age of the Modelo Formation. Based on average geothermal gradients for the Ventura and Los Angeles basins and an assumed thrust fault dip of 20°, observed apparent exhumation rates are

The effect of ageing in phosphate-containing solution of bioactive calcium-silicate cements on the chemistry, morphology and topography of the surface, as well as on in vitro human marrow stromal cells viability and proliferation was investigated. A calcium-silicate cement (wTC) mainly based on dicalcium-silicate and tricalcium-silicate was prepared. Alpha-TCP was added to wTC to obtain wTC-TCP. Bismuth oxide was inserted in wTC to prepare a radiopaque cement (wTC-Bi). A commercial calcium-silicate cement (ProRoot MTA) was tested as control. Cement disks were aged in DPBS for 5 h ('fresh samples'), 14 and 28 days, and analyzed by ESEM/EDX, SEM/EDX, ATR-FTIR, micro-Raman techniques and scanning white-light interferometry. Proliferation, LDH release, ALP activity and collagen production of human marrow stromal cells (MSC) seeded for 1-28 days on the cements were evaluated. Fresh samples exposed a surface mainly composed of calcium-silicate hydrates CSH (from the hydration of belite and alite), calcium hydroxide, calcium carbonate, and ettringite. Apatite nano-spherulites rapidly precipitated on cement surfaces within 5 h. On wTC-TCP the Ca-P deposits appeared thicker than on the other cements. Aged cements showed an irregular porous calcium-phosphate (Ca-P) coating, formed by aggregated apatite spherulites with interspersed calcite crystals. All the experimental cements exerted no acute toxicity in the cell assay system and allowed cell growth. Using biochemical results, the scores were: fresh cements>aged cements for cell proliferation and ALP activity (except for wTC-Bi), whereas fresh cementsapatite nano-spherulites; (2) the alpha-TCP doped cement aged for 28 days displayed the highest bioactivity and cell proliferation; (3) the deleterious effect of bismuth on cell

The Castle Mountain fault is a 200-km-long, right-lateral fault that forms the northern boundary of the Cook Inlet basin and Matanuska Valley, Alaska. Fault gouge and fault rock at six localities contain the clay minerals illite, smectite, chlorite, and interstratified illite/smectite. At one locality, gouge contains deformed illite/smectite with very little wall rock chlorite contamination. Fine (<0.03 μm), medium (0.03-0.2 μm), and coarse (0.2-2.0 μm) illite/smectite from this site were dated using 40Ar/ 39Ar micro-encapsulation and laser microprobe methods. Total gas ages for the three size fractions are 28.21±0.12, 32.42±0.11 and 36.24±0.08 Ma for fine to coarse sizes respectively. Argon retention ages obtained from 40Ar and 39Ar retained in the three size fractions of illite at room temperature during neutron irradiation are 37.36±0.15, 42.11±0.14 and 47.20±0.10 respectively. Apatite fission track ages were measured in arkose at a locality on the fault 60 km west of the gouge locality. Three samples of arkose were dated: one within 10 m of the fault core, one 170 m from the fault, and one 335 m from the fault. The sample nearest to the fault yielded an age of 29.3±2.8 Ma, but it only had four track lengths at 10-13 μm. Two apatite grains from the intermediate sample yielded a pooled age of 34.3±6.1 Ma. The distant sample (25 grains counted, 101 track lengths) yielded an age of 32.0±2.9 Ma. This sample has a broad distribution of track lengths and a broad distribution of individual grain ages ranging from 14.8±5.1 to 67.8±8.8 Ma. Monte Carlo modeling of the apatite age and track length data is consistent with hydrothermal mineralization at 37-39 Ma followed by rapid uplift and cooling after 10 Ma. The 40Ar/ 39Ar total gas ages (K-Ar) are minimum ages, and the argon retention ages are maximum ages. The thermal model derived from the fission track data, and the argon retention age for the finest illite fraction of ˜37 Ma date a hydrothermal

The aim of a recent paper was to recognize the chemical and structural changes in apatites, which form both the enamel and the dentin of the human tooth. The aim was achieved by scrutinizing the linear elemental profiles along the cross-sections of human molar teeth. Essentially, the task was accomplished with the application of the Electron Probe Microanalysis method and with some additional studies by Micro-Raman spectrometry. All the trends in linear profiles were strictly determined. In the enamel zone they were either increasing or decreasing curves of exponential character. The direction of the investigations was to start with the tooth surface and move towards the dentin-enamel junction (DEJ). The results of the elemental studies were more visible when the detected material was divided, in an arbitrary way, into the prevailing "core" enamel (˜93.5% of the total mass) and the remaining "overbuilt" enamel. The material in the "core" enamel was fully stable, with clearly determined chemical and mechanical features. However, the case was totally different in the "overbuilt enamel", with dynamic changes in the composition. In the "overbuilt" layer Ca, P, Cl and F profiles present the decaying distribution curves, whereas Mg, Na, K and CO 32- present the growing ones. Close to the surface of the tooth the mixture of hydroxy-, chlor- and fluor-apatite is formed, which is much more resistant than the rest of the enamel. On passing towards the DEJ, the apatite is enriched with Na, Mg and CO 32-. In this location, three of six phosphate groups were substituted with carbonate groups. Simultaneously, Mg is associated with the hydroxyl groups around the hexad axis. In this way, the mechanisms of exchange reactions were established. The crystallographic structures were proposed for new phases located close to DEJ. In the dentin zone, the variability of elemental profiles looks different, with the most characteristic changes occurring in Mg and Na concentrations. Mg

Following an evaluation of potential Sr-90 treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N Area will include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary (most likely phytoremediation). Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing Sr-90 flux to the river at a reasonable cost. In July 2005, aqueous injection, (i.e., the introduction of apatite-forming chemicals into the subsurface) was endorsed as the interim remedy and selected for field testing. Studies are in progress to assess the efficacy of in situ apatite formation by aqueous solution injection to address both the vadose zone and the shallow aquifer along the 300 ft of shoreline where Sr-90 concentrations are highest. This report describes the field testing of the shallow aquifer treatment.

We combine apatite fission track ages and track-length measurements with apatite (U-Th)/He ages to test the hypothesis that active near-surface faulting is absent at the transition between the Higher and Lower Himalayan physiographic provinces in central Nepal. Fifteen samples define a 2.5-km-long, nearly constant-elevation transect that crosses the largest knickzone on the Modi River in central Nepal. This knickzone could have resulted from modern faulting near the ancient Main Central thrust or from river incision following landslide dam breaching. Apatite fission track ages from the transect are generally ca. 1 Ma, and apatite He ages, selected by considering He concentrations, are 0.5-0.8 Ma. There is no discernable age difference between any of the samples outside 2σ uncertainty. Cooling rates are >100°C/Myr and are uniform across the sample transect. We calculate an average exhumation rate of ˜3 mm/yr across the region, with rates deduced from the fission track data equal to those extracted from the He ages. According to our new data, no fault in our study area has undergone a time-averaged slip rate faster than 4 mm/yr during the past 1 Myr.

It has previously been demonstrated that apatite may be coated on the surface of titanium (Ti) at room temperature when the titanium is blasted with apatite powder. This method is known as the blast coating (BC) method. In this study, the osteoconductivity and tissue response to Ti implants blast-coated with apatite (BC implants) were evaluated using apatite-coated Ti implants produced using the flame spraying (FS) method (FS implants) and pure Ti implants as a control. Initial evaluation using simulated body fluid demonstrated higher osteoconductivity in BC implants than in FS implants. Therefore, specimens were implanted in rat tibias for 1, 3 and 6 weeks. At one week after implantation, BC implants showed much higher bone contact ratio when compared with FS implants; the bone contact ratio of BC implants was 75.7%, while the FS and pure Ti implants had ratios of 30.8% and 5.5%, respectively. The difference in bone contact ratio between BC and FS implants decreased with implantation time and the ratios were equal after 6 weeks. In conclusion, BC implants show higher osteoconductivity than FS implants, and thus BC implants are beneficial for early fixation of implants to bone tissue. PMID:21778611

Rare earth silicates with the structure of apatite are attracting considerable interest since they show oxygen ion conductivities higher than that of yttria-stabilized zirconia (YSZ) at moderate temperature. Based on the hydrothermal synthesis we presented a simple one step process for the direct preparation of the pure and the high crystalline nanosized rare earth silicates with the structure of apatite under a mild condition (230 {sup o}C). Since the preparation of the high crystalline silicon based rare earth apatites is performed at high temperature previously and accompanied by subsequent process of grinding, results of this work provide a promising alternative of the existing methodology. Furthermore, due to the relatively low temperature of the preparation of these materials, high doping of monovalent cation can be done, which was not achieved before. -- Graphical abstract: A simple one step process for the preparation of the rare earth silicates with the structure of apatite under a mild condition (230 {sup o}C) is presented. The process is based on the hydrothermal synthesis and the obtained powder materials are pure, high crystalline and with nanosize. Display Omitted

The role of volatiles in the petrogenesis of alkaline intra-plate magmas has been the subject of an increasing number of experimental studies. The study of naturally occurring rocks and their volatile contents is often complicated by syn- and post-eruptive degassing and alteration processes. Minerals that incorporate volatiles into their structure such as apatites are often more faithful recorders of the pre-eruptive volatile budget. The Hegau volcanic field in Southwest Germany is part of the Central European Volcanic Province, lies around 60-70 km to the east of the Upper Rhine graben and of Miocene age. Three main lithological units can be distinguished (1) olivine melilites (2) phonolites and (3) the "Deckentuff" series referring to a series of diatreme-filling pipe breccias and lapilli tuff layers. Carbonatites occur subordinately in the Hegau province. Earlier radiometric age dating suggested distinct phases of volcanic activity of Deckentuffs, melilites and phonolites with little overlap, but new apatite fission-track and (U-Th)/He age data suggest a synchronous activity. Apatite is an abundant accessory phase in the Deckentuff and phonolite series and we investigated its major, trace and volatile element composition by EPMA, SIMS and cathodoluminescence imaging. Pronounced core-rim zoning of apatite in places attests that diffusional equilibration was very limited and they likely retained their primary compositions. This allows us to trace the entire magmatic evolution of the Hegau province from its most primitive to most evolved products as well as resolve it in time by combining age dating with compositional analysis. Apatite compositions fall along the OH-F join with low Cl-contents (<0.5 wt%). Volatile contents (Cl, OH, S) are highest in most primitive compositions and decrease with further evolution while F increases. Multiple magmatic cycles can be discerned with a general trend to the more evolved phonolite compositions toward the end of volcanic

Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.

Cementless fixation for the tibial component in total knee arthroplasty (TKA) remains problematic. Peri-Apatite (PA), a solution-deposited hydroxyapatite, is under investigation as an option for improving the fixation of cementless tibial components. In this study, radiostereometric analysis was used to document implant migration in 48 dogs that underwent TKA with cementless, PA-coated, or cemented tibial components. Migration at 12 weeks was similar in the 2 groups. At 12 months, there was greater migration in the PA-coated group, but the difference between the 2 groups was below the threshold considered clinically significant. In this canine TKA model, cementless fixation with PA performed less well than did cemented fixation, but not to a degree that would make a clinical difference in the short term. PMID:22364907

The use of dynamic compaction and isostatic compression to consolidate calcium phosphate powder loaded with a therapeutic agent avoids a sintering step that could destroy the drug. The present study applied these consolidation methods to vancomycin-loaded calcium-deficient apatite powder, using three granulometric fractions (40-80, 80-200 and 200-500 micrometer). In vitro release profiles were determined via an original system derived from low-pressure liquid chromatography. The biological activity of vancomycin was measured by an in vitro standardized bacteriologic assay, which showed that the drug is completely active after association with calcium phosphate. Regardless of the consolidation method and granulometric fraction used, release profiles were not significantly different and therefore adaptable to injectable suspensions. PMID:12527267

Melting experiments (P = 6.9 kbar, T = 850-950 deg C, NNO is less than fO2 is less than HM) were done on mafic to felsic charnockites, a dioritic gneiss, and a felsic garnet granulite, all common rock types in the Grenville basement of eastern North America. A graphite-bearing granulite gneiss did not melt. Water (H2O(+) = 0.60 to 2.0 wt %) is bound in low-grade, retrograde metamorphic minerals and is consumed during the earliest stages of melting. Most melts are water-undersaturated. Melt compositions range from metaluminous, silicic granodiorite (diorite starting composition) to peraluminous or weakly metaluminous granites (all others). In general, liquids become more feldspathic, less silicic, and less peraluminous and are enriched in FeO, MgO, and TiO2 with increasing temperature. Residual feldspar mineralogy controls the CaO, K2O, and Na2O contents of the partial melts and the behavior of these elements can be used, particularly if the degree of source melting can be ascertained, to infer some aspects of the feldspar mineralogy of the source. K-feldspar, a common restite phase in the charnockite and granulite (but not the diorite) should control the behavior of Ba and, possibly, Eu in these systems and yield signatures of these elements that can distinguish source regions and, in some cases, bulk versus melt assimilation. Apatite, a common restite phase, is enriched in rare earth elements (REE), especially middle REE. Retention of apatite in the restite will result in steep, light REE-enriched patterns for melts derived from the diorite and charnockites.

Apatite and zircon fission track thermochronology studies are applied to basement and sedimentary rocks from the Sul-Rio-Grandense Shield to unravel the tectonic history of the onshore southernmost Brazilian margin. The Sul-Rio-Grandense Shield is a major geotectonic feature of southernmost Brazil that includes Paleoproterozoic basement areas and Neoproterozoic fold belts linked to the Brasiliano/Pan-African orogeny. Crustal reworking and juvenile accretion events related to this cycle were dated in the region between 900 and 500 Ma and were responsible for the assembly of southwestern Gondwana in southeastern South America. Apatite fission track (AFT) ages range from 340 ± 33 to 77 ± 6 Ma and zircon fission track (ZFT) ages range from ca. 386 to 210 Ma. Based on thermal history modeling, the most part of the samples record an early cooling event during the Carboniferous, which reflect the main tectonic activity of the final stages of the Gondwanides at the Pacific margin of West Gondwana. Subsequently, the Permo-Triassic cooling event is related to the last stages of the Gondwanides, with convergence along the southern border of Western Gondwana and consequent reactivation of N-S and NE-SW trending basement structures. The onset of initial breakup of southwestern Gondwana with opening of the South Atlantic Ocean is mostly recorded in the eastern terrain and ZFT ages show that the temperature during this period was high enough for total or at least partial resetting of fission tracks in zircon. The last cooling event of the Sul-Rio-Grandense Shield records the final breakup between South America and Africa, which began during the Late Cretaceous. However, the Cenozoic rapid cooling episode probably is a result of plate adjustment after breakup and neotectonic reactivation of faults associated with South Atlantic rift evolution.

Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

We reconstruct the history of denudation and landscape evolution of the northern East- Brazilian continental margin using apatite fission-track thermochronology and thermal history modeling. This part of the Brazilian Atlantic margin is morphologically characterized by inland and coastal plateaus surrounding a wide low-lying inland region, the Sertaneja Depression. The apatite fission track ages and mean track lengths vary from 39 ± 4 to 350 ± 57 Ma and from 10.0 ± 0.3 to 14.2 ± 0.2 μm, respectively, implying a protracted history of spatially variable denudation since the Permian at relatively low rates (<50 m My-1). The Sertaneja Depression and inland plateaus record Permian-Early Jurassic (300-180 Ma) denudation that precedes rifting of the margin by > 60 Myrs. In contrast, the coastal regions record up to 2.5 km of Late Jurassic-Early Cretaceous (150-120 Ma) denudation, coeval with rifting of the margin. The samples from elevated coastal regions, the Borborema Plateau and the Mantiqueira Range, record cooling from temperatures above 120 °C since the Late Cretaceous extending to the Cenozoic. We interpret this denudation as related to post-rift uplift of these parts of the margin, possibly resulting from compressional stresses transmitted from the Andes and/or magmatism at that time. Several samples from these areas also record accelerated Neogene (<30 Ma) cooling, which may record landscape response to a change from a tropical to a more erosive semi-arid climate during this time. The inferred denudation history is consistent with the offshore sedimentary record, but not with evolutionary scenarios inferred from the recognition of “planation surfaces” on the margin. The denudation history of the northeastern Brazilian margin implies a control of pre-, syn- and post-rift tectonic and climatic events on landscape evolution.

Global increase in rare earth demand and consumption has led to further understanding their beneficiation and recovery. Monazite is the second most important rare earth mineral that can be further exploited. In this study, the surface chemistry of monazite in terms of zeta potential, adsorption density, and flotation response by microflotation using octanohydroxamic acid is determined. Apatite, ilmenite, quartz, rutile, and zircon are minerals that frequently occur with monazite among other minerals. Hence they were chosen as gangue minerals in this study. The Iso Electric Point (IEP) of monazite, apatite, ilmenite, quartz, rutile, and zircon are 5.3, 8.7, 3.8, 3.4, 6.3, and 5.1 respectively. The thermodynamic parameters of adsorption were also evaluated. Ilmenite, rutile and zircon have high driving forces for adsorption with DeltaGads. = 20.48, 22.10, and 22.4 kJ/mol respectively. The free energy of adsorption is 14.87 kJ/mol for monazite. Adsorption density testing shows that octanohydroxamic acid adsorbs on negatively charged surfaces of monazite and its gangue minerals which indicates chemisorption. This observation was further confirmed by microflotation experiments. Increasing the temperature to 80°C raises the adsorption and flotability of monazite and gangue minerals. This does not allow for effective separation. Sodium silicate appeared to be most effective to depress associated gangue minerals. Finally, the fundamentals learned were applied to the flotation of monazite ore from Mt. Weld. However, these results showed no selectivity due to the presence of goethite as fine particles and due to a low degree of liberation of monazite in the ore sample.

The orientation of nanoscale mineral platelets was quantitatively evaluated in relation to the shape of lacunae associated with partially embedded osteocytes (osteoblastic-osteocytes) on the surface of deproteinised trabecular bone of adult sheep. By scanning electron microscopy and image analysis, the mean orientation of mineral platelets at the osteoblastic-osteocyte lacuna (Ot.Lc) floor was found to be 19° ± 14° in the tibia and 20° ± 14° in the femur. Further, the mineral platelets showed a high degree of directional coherency: 37 ± 7% in the tibia and 38 ± 9% in the femur. The majority of Ot.Lc in the tibia (69.37%) and the femur (74.77%) exhibited a mean orientation of mineral platelets between 0° and 25°, with the largest fraction within a 15°-20° range, 17.12 and 19.8% in the tibia and femur, respectively. Energy dispersive X-ray spectroscopy and Raman spectroscopy were used to characterise the features observed on the anorganic bone surface. The Ca/P (atomic %) ratio was 1.69 ± 0.1 within the Ot.Lc and 1.68 ± 0.1 externally. Raman spectra of NaOCl-treated bone showed peaks associated with carbonated apatite: ν1, ν2 and ν4 PO4(3-), and ν1 CO3(2-), while the collagen amide bands were greatly reduced in intensity compared to untreated bone. The apatite-to-collagen ratio increased considerably after deproteinisation; however, the mineral crystallinity and the carbonate-to-phosphate ratios were unaffected. The ~19°-20° orientation of mineral platelets in at the Ot.Lc floor may be attributable to a gradual rotation of osteoblasts in successive layers relative to the underlying surface, giving rise to the twisted plywood-like pattern of lamellar bone. PMID:26472430

The evolution of the rift shoulder and the sedimentary sequence of the Morondava basin in western Madagascar was mainly influenced by a Permo-Triassic continental failed rift (Karroo rift), and the early Jurassic separation of Madagascar from Africa. Karroo deposits are restricted to a narrow corridor along the basement-basin contact and parts of this contact feature a steep escarpment. Here, apatite fission track (AFT) analysis of a series of both basement and sediment samples across the escarpment reveals the low-temperature evolution of the exhuming Precambrian basement in the rift basin shoulder and the associated thermal evolution of the sedimentary succession. Seven basement and four Karroo sediment samples yield apparent AFT ages between ˜330 and ˜215 Ma and ˜260 and ˜95 Ma, respectively. Partially annealed fission tracks and thermal modeling indicate post-depositional thermal overprinting of both basement and Karroo sediment. Rocks presently exposed in the rift shoulder indicate temperatures of >60°C associated with this reheating whereby the westernmost sample in the sedimentary plain experienced almost complete resetting of the detrital apatite grains at temperatures of about ˜90-100°C. The younging of AFT ages westward indicates activity of faults, re-activating inherited Precambrian structures during Karroo sedimentation. Furthermore, our data suggest onset of final cooling/exhumation linked to (1) the end of Madagascar's drift southward relative to Africa during the Early Cretaceous, (2) activity of the Marion hot spot and associated Late Cretaceous break-up between Madagascar and India, and (3) the collision of India with Eurasia and subsequent re-organization of spreading systems in the Indian Ocean.

Ultra-high spatial resolution ion microprobe depth-profiles of pre-3.9 Ga terrestrial zircons from the Jack Hills (Western Australia) have the potential to record a sharply elevated impactor flux to the inner planets at ca. 3.95 Ga termed the Late Heavy Bombardment (LHB). A putative signature of this is in the form of ~3.95 Ga, 2 to 4 μm mantles over the (oldest) igneous zircon cores (up to 4.3 Ga). These minute mantles show Pb-loss (up to 90% discordance) over narrow domains that could be the result of impact heating. Pre-3.9 Ga lunar zircon grains have not yet been depth-profiled, but it is evident from published spot analyses that grain cores preserve original igneous ages albeit with no clear super-imposition of later thermal events. However, the U-Pb systematics of apatites in the same lunar rocks were reset ca. 3.95 Ga. The motivation of this study is to explain the high degree of Pb (and other cation) loss over very short distances (<6 μm) in terrestrial zircons at ~3.9 Ga, the complete resetting of U-Pb isotope systematics of lunar apatites at approximately the same time, and to make predictions in preparation for depth-profile work on lunar samples. To accomplish these goals, we used existing models that simulate the thermal consequences of LHB, as well as established equations for cation diffusion in zircon and apatite. The main thermal model consists of (i) a stochastic cratering model which populates the surface with craters within constraints derived from the lunar cratering record, the size/frequency distribution of the asteroid belt, and dynamical models; (ii) analytical expressions that calculate a temperature field for each model crater; and (iii) three-dimensional thermal models of lunar and terrestrial lithospheres, where craters are allowed to cool by conduction in the subsurface and radiation at the surface. In addition, a high-resolution near-surface model was used to account for additional thermal pulses due to global deposition of hot

The low-temperature thermochronology has been an important tool to quantify geological process in passive continental margins. In this context, the Angolan margin shows evidence of a polycyclic post-rift evolution marked by different events of uplift, basin inversion and changes in sedimentation rates to the marginal basins, which have controlled the salt tectonics and the hydrocarbon deposits (1,2,3,4). To understand the post break-up evolution of the southwestern Angola margin, it were collected outcrop samples for apatite fission track (AFT) and (U-Th)/He analysis ranging in elevation from 79 m to 1675 m from the coast toward the interior plateau in a profile between Namibe and Lubango cities. The area lies on the edge of Central and Southern Atlantic segments a few kilometers northward the Walvis ridge and encompasses the Archean and Proterozoic basement rocks of the Congo craton. The AFT ages ranging from 120.6 ± 8.9 Ma to 328.8 ± 28.5 Ma and they show a trend of increasing age toward the Great Escarpment with some exceptions. The partial mean track lengths (MTLs) vary between 11.77 ± 1.82 μm to 12.34 ± 1.13 μm with unimodal track length distributions (TDLs). The partial (U-Th)/He ages ranging from 104.85 ± 3.15 Ma to 146.95 ± 4.41 Ma and show the same trend of increasing ages landward, little younger than the AFT ages, which could be interpreted as a fast exhumation episode in Late Jurassic - Early Cretaceous times. The thermal histories modelling has been constrained with the kinetic parameters Dpar (5) and c-axis angle (6) by the software Hefty (7). Both AFT and (U-Th)/He thermal histories modelling indicate three episodes of denudation/uplift driven cooling: (a) from Late Jurassic to Early Cretaceous, (b) a smallest one in the Late Cretaceous and (c) from Oligocene-Miocene to recent, which are compatible with geophysical data of the offshore Namibe basin that estimate the greater thickness of sediments formed in the first and third episodes

Clinopyroxene and apatite are found to trace metasomatic processes in nepheline-bearing clinopyroxenites (tilaites) from the igneous, mafic-ultramafic Uralian-Alaskan-type complexes of Kytlym and Nizhny Tagil, Ural Mountains, Russian Federation. The clinopyroxenites consist predominantly of coarse-grained, partially to totally altered clinopyroxene phenocrysts in a matrix of fine-grained olivine, clinopyroxene, plagioclase, K-feldspar, and nepheline. Apatite occurs as idiomorphic inclusions (<25 μm) in the clinopyroxene and as xenomorphic grains in the matrix. In the matrix, plagioclase is partially to totally replaced by a fine-grained symplectitic intergrowth of K-feldspar and nepheline most likely due to the influx of an K2O-, Na2O-, and Al2O3-bearing fluid. During conversion of the plagioclase, CaO and SiO2 were partitioned into the fluid. Altered areas in the clinopyroxene phenocrysts are characterized by the redistribution of major and trace elements. This includes depletion in Mg, Rb, and Sr and enrichment in Al, Na, Ba, U, Th, REE except Eu, and HFSE compared to the original magmatic areas in the clinopyroxene. Apatite inclusions in the altered areas of the clinopyroxene and in the matrix are enriched in Cl relative to apatite inclusions in the unaltered areas of clinopyroxene. It is proposed that these rocks experienced a two-stage metasomatic process. Stage 1 was the partial to total alteration of plagioclase to K-feldspar and nepheline due to interaction with an infiltrating (K,Na)Cl-rich brine (most likely late magmatic) with an Al component, which enriched the fluid in CaCl2. Stage 2 consisted of the partial to total chemical alteration of the original magmatic clinopyroxene by this now CaCl2-enriched fluid through the mechanism of coupled dissolution-reprecipitation. This process also chemically altered the apatite inclusions from fluor-chlorapatite to chlor-fluorapatite and redistributed as well as partially removed the titanomagnetite inclusions in

The morpho-tectonic history of the western South African continental margin and interior plateau remains enigmatic. Recent investigations of offshore sediment accumulation and interpretations of onshore structural and geomorphological observations have highlighted the complex geological evolution of South Africa throughout the Mesozoic and Cenozoic. Moreover, advances in geodynamic modelling approaches have explored the crustal response to varying styles of rifting and the influence of mantle upwelling beneath the African plate. These geological observations and models, however, require validation from quantitative constraints on the surface response (i.e. uplift and erosion) to syn- and post rift thermal and tectonic processes Over the last two decades, low temperature thermochronometry, particularly apatite fission track analysis (AFTA) and apatite (U-Th)/He, have been effective tools in providing these constraints by tracking the time-temperature history of rocks through c. 60 - 110°C and 80 - 40°C, respectively. The unique ability of AFTA to constrain both the timing and nature of sample cooling rests largely on the sensitivity of fission track annealing to temperature. Here, we present new AFT data from a suite of samples across the entire western continental margin of South Africa which contributes to a now extensive AFT dataset spanning the entire sub-continent. This dataset broadly invokes at least two discrete episodes of cooling driven by km scale denudation at c. 130 Ma, following rifting and break up of West Gondwana, and 90 Ma as a response to renewed tectonic uplift. However, the apparent lack of correlation of AFT age with elevation or with distance from the coast highlight the spatial and temporal variability of post-rift cooling that may be related to Mid-Cretaceous structural reactivation along the margin. We also present thermal history modelling using the Bayesian transdimensional inverse modelling approach of QTQt (Gallagher, 2012). Modelling

The Early Triassic climate is conventionally interpreted to have been warm and ice-free. During this time, three globally recognized depositional sequences developed in response to My-scale eustatic sea-level changes. The rates of My-scale sea-level rise and fall are too fast to attribute to changes in mid-ocean ridge activity and too slow to attribute to typical ~20-400 ky orbital cycles that drive glacio-eustasy. Previous studies in the Middle Devonian, Late Cretaceous, and Middle Eocene greenhouse climates have suggested that significant glacio-eustatic sea-level changes were responsible for sequence development. This suggests that these particular greenhouse periods were not uniformly warm and ice-free. We are testing the hypothesis that My- and orbital-scale sea-level changes in the Early Triassic (Smithian) were driven by glacio- and/or thermo-eustasy. To test this hypothesis, Smithian marine successions from two localities in the western United States (Lower Thaynes Formation) were described on a bed-by-bed basis to provide facies and depositional environment interpretations, as well as put the sections into a sequence stratigraphic framework. Samples were collected from both locations for high-resolution (~1-10 m) oxygen isotopic analysis of conodont apatite. Conodont elements are excellent biostratigraphic indicators and the apatite is less susceptible to diagenetic alteration than carbonate minerals, making conodont apatite a reliable proxy for determining changes in ice volume and seawater temperatures in deep time. In northeastern Utah (Weber Canyon), the Smithian sequence (~240 m) is composed of a mixed carbonate-siliciclastic lowstand systems tract (>40 m) and transgressive systems tract (~110 m), a black shale maximum flooding zone (~15 m), and a carbonate-dominated highstand systems tract (~75 m). In western Utah (Confusion Range), the sequence is composed of a coarse-grained, carbonate-dominated transgressive systems tract (>40 m) and a mixed

The synthesis of chloro-vanadato-apatites M5(VO 4) 3Cl ( M = Ca, Sr, Ba) in a two step solid state procedure is reported. IR spectra show a considerable shift of the frequencies attributed to the tetrahedral group to lower energies compared with the phosphato-apatites. The structure of these compounds is determined by powder diffraction data and refined using Rietveld methods. An elaborate analysis of the data shows that the chloride anions are to be found at different positions along a channel along [001] with varying probability. They are fairly well localised in the case of the Sr and the Ba compound. In the Ca compound they are spread over a larger region along c. A refinement according to a new concept of "metric distortion" gives a good fit of the data and indicates that the delocalisation of electron density seen in a Difference-Fourier plot is best described by a static picture of disorder.

The Finero Phlogopite-Peridotite (FPP) is a mantle unit outcropping in the northernmost tip of the Ivrea-Verbano Zone (IVZ, Southern Alps). It shows a virtually complete recrystallization due to pervasive to channelled melt migration. The pervasive metasomatism formed a main lithologic association constituted by phlogopite harzburgites associated to phlogopite pyroxenites (mainly olivine-websterites, websterites and orthopyroxenites). These lithologies are also rich in amphibole and do not show significant chemical gradients among them (Zanetti et al., 1999). The channelled migration stages formed dunite bodies, which sometimes contain stratiform chromitites and, more rarely, pyroxenite layers similar to those associated to phlogopite harzburgite. The FPP also shows a discrete number of other, subordinate rock-types, which are characterised by the presence of apatite usually associated to carbonates (i.e. calcite or dolomite) and exhibit marked modal and chemical gradients with respect to the host phlogopite harzburgite. Examples of these lithologies are apatite-dolomite-bearing wehrlites and harzburgites (e.g. Zanetti et al. 1999; Morishita et al., 2008), apatite-calcite zircon-syenites and hornblendites. Ar-Ar amphibole analysis and U-Pb zircon and apatite data return Triassic ages for these rocks, which have been considered to document the time of melt/fluid injection. Notwithstanding the apparent mineralogical and chemical differences with the main lithologic sequences, apatite-carbonates-bearing rocks have been frequently interpreted as cogenetic to phlogopite harzburgites. To debate the petrogenesis of these rocks, a detailed field, petrological and geochemical investigation has been carried out on a swarm of apatite-calcite-bearing gabbroic veins that randomly cut the main lithologic association. Preliminary investigation evidenced as these veins show complex metasomatic haloes and a symmetric internal layering, characterised by crystallisation of magmatic

Following an evaluation of potential strontium-90 (90Sr) treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, the U.S. Department of Energy (DOE), Fluor Hanford, Inc. (now CH2M Hill Plateau Remediation Company [CHPRC]), Pacific Northwest National Laboratory, and the Washington State Department of Ecology agreed that the long-term strategy for groundwater remediation at the 100-N Area should include apatite as the primary treatment technology. This agreement was based on results from an evaluation of remedial alternatives that identified the apatite permeable reactive barrier (PRB) technology as the approach showing the greatest promise for reducing 90Sr flux to the Columbia River at a reasonable cost. This letter report documents work completed to date on development of a high-concentration amendment formulation and initial field-scale testing of this amendment solution.

Plasma electrolytic oxidation (PEO) was used to make a multifunctional porous titanium oxide (TiO2) coating on a titanium substrate. The key finding of this study is that a highly crystalline TiO2 coating can be made by performing the PEO in an ammonium acetate (CH3COONH4) solution; the PEO coating was formed by alternating between rapid heating by spark discharges and quenching in the solution. The high crystallinity of the TiO2 led to the surface having multiple functions, including apatite forming ability and photocatalytic activity. Hydroxyapatite formed on the PEO coating when it was soaked in simulated body fluid. The good apatite forming ability can be attributed to the high density of hydroxyl groups on the anatase and rutile phases in the coating. The degradation of methylene blue under ultraviolet radiation indicated that the coating had high photocatalytic activity. PMID:24094199

Apatite fission-track (AFT) ages from the Iberian Massif, along the northern coastal region in Galicia are presented. The study aims at unravelling the exhumation history of this higher topography coastal region, the so-called Rías Altas region, next to the northern Iberian margin. The rough topography region is bound to the south by the WNW-ESE trending As Pontes dextral strike-slip fault zone. This fault was active since ca. 30 Ma (Rupelian) up to ca. 21 Ma (Aquitanian). The area comprises mainly Late Proterozoic to Paleozoic metamorphic and igneous rocks from the hinterland of the Variscan orogen. A N-S AFT ages profile from the coast to the southern block of the As Pontes fault reveal progressively younger ages toward the south with the oldest ages (242 ± 12 Ma) located near the coast and the youngest age being 124 ± 7 Ma. The AFT ages at both sides of the As Pontes fault in samples taken at the same elevation are similar within error (124 ± 7and 127 ± 7 Ma) indicating that this strike-slip fault did not cause significant differential exhumation during Oligocene-Early Miocene times. Another important feature shown by these data is that the age-elevation relationship (AER) is negative, the youngest ages being located at the highest elevation (ca. 1000 m. a. s. l). This agrees with recent published data from the easternmost part of the present study area and is an indication of Post-Early Cretaceous long residence time within the upper 2 or 3 km of the crust at temperatures lower than those of the apatite partial annealing zone (60 to 120°C). We interpret the registered exhumation history as mostly related to rifting processes in Pre-Early Cretaceous times. Possibly recording surface processes associated to the two stage rifting episodes in the Triassic and in the Late Jurassic-Early Cretaceous that culminated with formation of the north Iberian Margin. The negative AER suggests that since Early Cretaceous times the whole area underwent topographic changes

The aim of this study is to provide a quantitative overview of Mesozoic-Cenozoic morphotectonic evolution and sediment supply to the northeast Brazilian margin. Landscape evolution and denudation histories for the northeastern Brazilian continental margin (Sergipe, Alagoas, Bahia, and Espírito Santo states) were detailed by apatite fission track thermochronology and thermal-history modeling and related with the sedimentological record of the offshore basins of the passive margin for a comparison with their denudational history. Approximately one hundred basement samples were analyzed from the coast to the inland of the Brazilian margin. The apparent fission track ages vary from 360 to 61 Ma and confined fission track lengths vary between 10 and 14.6 µm, indicating that not all of the samples recorded the same cooling events. The results of apatite fission track ages indicate that the area has been eroded regionally since the Mesozoic (< 250 Ma) and suggest that at less 4 km of overburden has been eroded regionally since the late Cretaceous (< 120 Ma) at a rate of 120 to 15 m/Ma. Two-stage of erosion process is deduced from simulated cooling histories for each sector. The Permian-Early Jurassic exhumation is restricted to the area of the Sertaneja Depression, besides the Diamantina Plateau. During this time, denudation rates are generally <20 m My-1 and record up to 1.5 km of denudation. Pre-rift sedimentation is recorded in the Camamu-Almada, Recôncavo, and Sergipe-Alagoas basins. Samples from the Conquista and Borborema Plateaus, and Mantiqueira Range record a Cretaceous-Paleogene onset of exhumation. This timing is consistent with the offshore sedimentary record, wherein a large clastic wedge started forming in the northeastern Sergipe-Alagoas basin, which suggests Sergipe-Alagoas basin records drainage reorganization and extension of the São Francisco River catchment. Interestingly, the Camamu basin, adjacent to the section of the margin does not record syn

The thermal history of the Kola Peninsula area of NE Fennoscandia remains almost fully unknown because of the absence of any thermochronological data such as apatite and/or zircon fission track or (Usbnd Th)/He ages. In order to fill this gap and to constrain the post-Devonian erosion and exhumation history of this region, we present the results of apatite fission track (AFT) dating of eleven samples selected from the cores taken from different depths of the northern part of the Khibina intrusive massif. The Rbsbnd Sr isochron age of this alkaline magmatic complex which is located at the center of Kola Peninsula is 368 + 6 Ma (Kramm and Kogarko, 1994). Samples were analyzed from depths between + 520 and - 950 m and yielded AFT ages between 290 and 268 Ma with an age uncertainty (1σ) of between ± 19 Ma (7%) and ± 42 Ma (15%). Mean track lengths (MTL) lie between 12.5 and 14.4 μm. Inverse time-temperature modeling was conducted on the age and track length data from seven samples of the Khibina massif. Thermal histories that best predict the measured data from three samples with the most reliable data show three stages: (1) 290-250 Ma-rapid cooling from > 110 °C to 70 °C/50 °C for lower/upper sample correspondingly; (2) 250-50 Ma-a stable temperature stage; (3) 50-0 Ma-slightly increased cooling rates down to modern temperatures. We propose that the first cooling stage is related to late-Hercynian orogenesis; the second cooling stage may be associated with tectonics accompanying with opening of Arctic oceanic basin. The obtained data show that geothermal gradient at the center of Kola Peninsula has remained close to the modern value of 20 °C/km for at least the last 250 Myr. AFT data show that the Khibina massif has been exhumed not more then 5-6 km in the last 290 Myr.

The timing and source of deformation responsible for formation of the Sierra Madre de Chiapas (south Mexico) are unclear. To address this, apatite fission track and U-Th-He thermochronometry, combined with zircon U-Pb dating, were performed on bedrock and sedimentary samples of the Sierra Madre de Chiapas to discern timing of exhumation and identify sediment source areas. The U-Pb results show that Paleocene-Eocene terrigenous units outcropping at the northern section of the Sierra were mostly derived from Grenville (˜1 Ga) basement whereas the internal sections of the chain yield mainly Permian to Triassic ages (circa 270-230 Ma) typical of the Chiapas massif complex. Grenville-sourced sediments are most probably sourced by the Oaxacan block or the Guichicovi complex and were deposited to the north of the Sierra in a foreland setting related to a Laramide deformation front. Other possibly source areas may be related to metasedimentary units widely documented at the south Maya block such as the Baldi unit. The apatite fission track and U-Th-He data combined with previously published results record three main stages in exhumation history: (1) slow exhumation between 35 and 25 Ma affecting mainly the Chiapas massif complex; (2) fast exhumation between 16 and 9 Ma related to the onset of major strike-slip deformation affecting both the Chiapas massif complex and Chiapas fold-and-thrust belt; and (3) a 6 to 5 Ma period of rapid cooling that affected the Chiapas fold-and-thrust belt, coincident with the landward migration of the Caribbean-North America plate boundaries. These data suggest that most of the topographic growth of the Sierra Madre de Chiapas took place in the middle to late Miocene. The new thermochronological evidence combined with stratigraphic and kinematic information suggests that the left-lateral strike-slip faults bounding the Chiapas fold-and-thrust belt to the west may have accommodated most of the displacement between the North American and

Mineral weathering is an important process in biogeochemical cycling because it releases nutrients from less labile pools (e.g., rocks) to the food chain. A field experiment was undertaken to determine the degree to which microbes - both fungi and bacteria - are responsible for weathering of Ca-bearing minerals. The experiment was performed at the Hubbard Brook Experimental Forest (HBEF) in the northeastern USA, where acid deposition has leached plant-available calcium from soils for decades. Trees obtain soil nutrients through root uptake as well as through mycorrhizal fungi with which they are symbiotically associated. These fungi extend their hyphae from the tree roots into the soil and exude organic acids that may enhance mineral dissolution. The two most common types of symbiotic fungal-tree associations are ectomycorrhizae, which are associated with spruce (Picea), fir (Abies), and beech (Fagus); and arbuscular mycorrhizae which are commonly associated with angiosperms, such as maples (Acer). To examine the role of fungi and bacteria in weathering of Ca- and/or P-bearing minerals, mesh bags containing sand-sized grains of quartz (as a control), quartz plus 1% wollastonite (CaSiO3), or quartz plus 1% apatite (Ca5(PO4)3F) were buried ~15 cm deep in mineral soil beneath American beech, sugar maple, and mixed spruce and balsam fir stands at the HBEF. Half of the bags were constructed of 50-μm mesh to exclude roots but allow fungal hyphae and bacteria to enter the bags; the remaining bags had 1-μm mesh to exclude fungi and roots but allow bacteria to enter. The bags were retrieved ~ 1, 2 or 4 years after burial. Microbial community composition and biomass in the mesh bags and surrounding soil were characterized and quantified using phospholipid fatty acid (PLFA) analysis. Fungal biomass in the soil and control bags did not differ significantly among stand types. In contrast, the degree of fungal colonization in apatite- and wollastonite-amended bags varied

The age and rate of exhumation of the British Mountains is tied to the timing of deformation in the Beaufort Sea, an active site for hydrocarbon exploration. This region contains a large portion of North America's oil and gas reserves. The British Mountains, the eastern extent of the Brooks Range in Alaska, include Paleogene structures that are the onshore portion of the Beaufort fold belt. In the Beaufort Sea, deformation is dominated by thin-skinned folding and thrusting of Paleocene to Oligocene sediments that is sourced from the British Mountains. Onshore, Paleogene deformation overprints multiple older structural events. The low temperature time history of the onshore Paleogene structures will be determined through U-Th/He dating of apatites (AHe). The results will contribute to better understanding of the timing of the maturation and migration of hydrocarbons in the Beaufort Sea. Previous work on the thermal history of northern Yukon and the North Slope of Alaska provides a regional framework for the region's low temperature-time history. These regional studies of the northern Yukon and Alaska yielded Paleocene to Eocene (60Ma - 40Ma) apatite fission track (AFT) cooling ages that progressively young to the north, consistent with geological evidence for northward propagating deformation. The British Mountains consist of Neoproterozoic to early Paleozoic marine sediments that are intruded by scattered Devonian plutons; both rock types will be included in the study. This study aims to improve the understanding of the Paleogene tectonic activity of the British Mountains and the deformation history of the Beaufort fold belt. The two data sets, existing AFT and new AHe results, will be both be included in the interpretation of the study area. We will present AHe data to better constrain the onshore exhumation and deformation rates at low temperatures (~60-90°C). A sampled transect through the British mountains, along the Firth River valley will provide good

Ce-doped Mg2Y8(SiO4)6O2 silicate apatite (Ce = 0.05 and 0.5) were irradiated with 1 MeV Kr2+ ion beam irradiation at different temperatures and their radiation response and the cation composition dependence of the radiation-induced amorphization were studied by in situ TEM. The two Ce-doped Mg2Y8(SiO4)6O2 silicate apatites are sensitive to ion beam induced amorphization with a low critical dose (0.096 dpa) at room temperature, and exhibits significantly different radiation tolerance at elevated temperatures. Ce concentration at the apatite AI site plays a critical role in determining the radiation response of this silicate apatite, in which the Ce3+ rich Mg2Y7.5Ce0.5(SiO4)6O2 displays lower amorphization susceptibility than Mg2Y7.95Ce0.05(SiO4)6O2 with a lower Ce3+ occupancy at the AI sites. The critical temperature (Tc) and activation energy (Ea) change from 667.5 ± 33 K and 0.162 eV of Mg2Y7.5Ce0.5(SiO4)6O2 to 963.6 ± 64 K and 0.206 eV of Mg2Y7.95Ce0.05(SiO4)6O2. We demonstrate that the radiation tolerance can be controlled by varying the chemical composition, and enhanced radiation tolerance is achieved by increasing the Ce concentration at the AI site.

Ten samples of crystalline rocks from the Bronson Hill anticlinorium in north central Massachusetts--south central Vermont yield Mesozoic apatite fission track cooling ages ranging from 98 [+-] 8 to 158 [+-] 24 Ma. Compositionally, the samples include a quartz-phyric rhyolite from the Ammonoosuc Volcanics, a pegmatite from the Kempfield Anticline, a gabbro from the Prescott Intrusive Complex, the Dry Hill and Fourmile Gneisses from the Pelham Dome, Swanzey Gneiss from the Keene Dome, Pauchaug Gneiss from the Warwick Dome, and the Monson Gneiss. Published U-Pb zircon analyses for the same samples yield ages of 613 [+-] 3 Ma for the Dry Hill Gneiss; 454--442 [+-] 3 Ma for the Swanzey, Pauchaug, Monson and Fourmile Gneisses; 453 [+-] 2 Ma for the Ammonoosuc Volcanics; and 407 [+-] 3/[minus]2 Ma for the Prescott Intrusive Complex gabbro (Tucker and Robinson, 1990). Apatite fission track ages are all reset and increase in apparent age eastward from the edge of the Deerfield-Hartford Basin, consistent with published apatite fission track ages from Jurassic sedimentary units within the Deerfield and Northern Hartford Basins. Mean track lengths ranged from 13.4 to 14.4 [mu]m with moderately large standard deviations. These track length distributions suggest relatively slow cooling through the track annealing range of 70--90 C and are consistent with track length distributions for sedimentary samples within the Deerfield and Northern Hartford Basins. The trend of increasing apatite fission track apparent age eastward from the basin margin suggests several interpretations: (1) differential uplift; (2) deeper burial in the basin and adjacent areas; (3) higher heat flow along the basin margin. Zircon fission track analyses are in progress to constrain maximum burial depths and should help differentiate between these models.

Ti-6Al-4V alloy is widely prevalent as a material for orthopaedic implants because of its good corrosion resistance and biocompatibility. However, the discrepancy in Young’s modulus between metal prosthesis and human cortical bone sometimes induces clinical problems, thigh pain and bone atrophy due to stress shielding. We designed a Ti-Nb-Sn alloy with a low Young’s modulus to address problems of stress disproportion. In this study, we assessed effects of anodic oxidation with or without hot water treatment on the bone-bonding characteristics of a Ti-Nb-Sn alloy. We examined surface analyses and apatite formation by SEM micrographs, XPS and XRD analyses. We also evaluated biocompatibility in experimental animal models by measuring failure loads with a pull-out test and by quantitative histomorphometric analyses. By SEM, abundant apatite formation was observed on the surface of Ti-Nb-Sn alloy discs treated with anodic oxidation and hot water after incubation in Hank’s solution. A strong peak of apatite formation was detected on the surface using XRD analyses. XPS analysis revealed an increase of the H2O fraction in O 1s XPS. Results of the pull-out test showed that the failure loads of Ti-Nb-Sn alloy rods treated with anodic oxidation and hot water was greater than those of untreated rods. Quantitative histomorphometric analyses indicated that anodic oxidation and hot water treatment induced higher new bone formation around the rods. Our findings indicate that Ti-Nb-Sn alloy treated with anodic oxidation and hot water showed greater capacity for apatite formation, stronger bone bonding and higher biocompatibility for osteosynthesis. Ti-Nb-Sn alloy treated with anodic oxidation and hot water treatment is a promising material for orthopaedic implants enabling higher osteosynthesis and lower stress disproportion. PMID:26914329

New zircon fission-track ages compliment published apatite fission-track ages in the Appalachian Basin to narrowly constrain its thermal history. Geologic evidence can only constrain timing of the thermal peak to be younger than late Pennsylvanian sediments ([approximately] 300 Ma) and older than Mesozoic sediments in the Newark and Gettysburg Basins ([approximately] 210 Ma). Apatite fission-track ages as old as 246 Ma require the Alleghanian thermal peak to have been pre-Triassic. Preliminary data on reset zircon fission-track ages from middle Paleozoic sediments range from 255 to 290 Ma. Zircon fission-track apparent ages from samples younger and structurally higher than these are not reset. Thus, the oldest reset zircon fission-track age constraints the time of the Alleghanian thermal peak to be earliest Permian. Rates of post-Alleghanian cooling have not been well-constrained by geologic data and could be very slow. The difference between apatite and zircon fission-track ages for most of the samples range from 100--120 m.y. reflecting Permo-Triassic cooling of only 1 C/m.y. However, one sample with one of the oldest apatite ages, 245 Ma, yields one of the younger zircon ages of 255 Ma. This requires cooling rates of 10 C/m.y. and uplift rates of [approximately] 0.5 mm/yr. Collectively, these data support an early Permian thermal peak and a two-stage cooling history, consisting of > 100 C cooling (> 8 km denundation) in the Permian followed by relatively slow cooling and exhumation throughout the Mesozoic.

Moulds of Baculites sp. are common in the Smoky Hill Member but only five known specimens contain connecting rings that have been preserved because of mineralisation by carbonate apatite. Analysis of four of these specimens suggests that the connecting rings were originally composed of organic material and were mineralised during early diagenesis. Thin sections and scanning electron microscopy demonstrate that the connecting rings had a two-layered structure consisting of a thick siphuncular wall and a thin pellicle. ?? 1985.

The bioactivity of calcium silicate mineral trioxide aggregate (MTA) cements has been attributed to their ability to produce apatite in presence of phosphate-containing fluids. This study evaluated surface morphology and chemical transformations of an experimental accelerated calcium-silicate cement as a function of soaking time in different phosphate-containing solutions. Cement discs were immersed in Dulbecco's phosphate-buffered saline (DPBS) or Hank's balanced salt solution (HBSS) for different times (1-180 days) and analysed by scanning electron microscopy connected with an energy dispersive X-ray analysis (SEM-EDX) and micro-Raman spectroscopy. SEM-EDX revealed Ca and P peaks after 14 days in DPBS. A thin Ca- and P-rich crystalline coating layer was detected after 60 days. A thicker multilayered coating was observed after 180 days. Micro-Raman disclosed the 965-cm(-1) phosphate band at 7 days only on samples stored in DPBS and later the 590- and 435-cm(-1) phosphate bands. After 60-180 days, a layer approximately 200-900 μm thick formed displaying the bands of carbonated apatite (at 1,077, 965, 590, 435 cm(-1)) and calcite (at 1,088, 713, 280 cm(-1)). On HBSS-soaked, only calcite bands were observed until 90 days, and just after 180 days, a thin apatite-calcite layer appeared. Micro-Raman and SEM-EDX demonstrated the mineralization induction capacity of calcium-silicate cements (MTAs and Portland cements) with the formation of apatite after 7 days in DPBS. Longer time is necessary to observe bioactivity when cements are immersed in HBSS. PMID:19943072

Ti-6Al-4V alloy is widely prevalent as a material for orthopaedic implants because of its good corrosion resistance and biocompatibility. However, the discrepancy in Young's modulus between metal prosthesis and human cortical bone sometimes induces clinical problems, thigh pain and bone atrophy due to stress shielding. We designed a Ti-Nb-Sn alloy with a low Young's modulus to address problems of stress disproportion. In this study, we assessed effects of anodic oxidation with or without hot water treatment on the bone-bonding characteristics of a Ti-Nb-Sn alloy. We examined surface analyses and apatite formation by SEM micrographs, XPS and XRD analyses. We also evaluated biocompatibility in experimental animal models by measuring failure loads with a pull-out test and by quantitative histomorphometric analyses. By SEM, abundant apatite formation was observed on the surface of Ti-Nb-Sn alloy discs treated with anodic oxidation and hot water after incubation in Hank's solution. A strong peak of apatite formation was detected on the surface using XRD analyses. XPS analysis revealed an increase of the H2O fraction in O 1s XPS. Results of the pull-out test showed that the failure loads of Ti-Nb-Sn alloy rods treated with anodic oxidation and hot water was greater than those of untreated rods. Quantitative histomorphometric analyses indicated that anodic oxidation and hot water treatment induced higher new bone formation around the rods. Our findings indicate that Ti-Nb-Sn alloy treated with anodic oxidation and hot water showed greater capacity for apatite formation, stronger bone bonding and higher biocompatibility for osteosynthesis. Ti-Nb-Sn alloy treated with anodic oxidation and hot water treatment is a promising material for orthopaedic implants enabling higher osteosynthesis and lower stress disproportion. PMID:26914329

The first globally significant phosphorous-rich deposits appear in the Paleoproterozoic at around 2 Ga, however, the specific triggers leading to apatite precipitation are debated. We examine phosphorous-rich rocks (up to 8 wt% P2O5) in 1.98-1.92 Ga old Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia. Phosphates in these rocks occur as locally derived and resedimented sand-to-gravel/pebble sized grains consisting of apatite-cemented muddy sediments. Phosphatic grains can be subdivided into four petrographic types (A-D), each has a distinct REE signature reflecting different early-to-late diagenetic conditions and/or metamorphic overprint. Pyrite containing petrographic type D, which typically has a flat REE pattern, negative Ce anomaly and positive Eu anomaly, is the best preserved of the four types and best records conditions present during apatite precipitation. Type D phosphatic grains precipitated under (sub)oxic basinal conditions with a significant hydrothermal influence. These characteristics are similar to Zaonega Formation phosphates of NW Russia's Onega Basin, and consistent with phosphogenesis triggered by the development of anoxic(sulfidic)-(sub)oxic redoxclines at shallow sediment depth during the Paleoproterozoic.

In order to improve techniques for provenance studies, and especially to address the question of sediment recycling, morphological changes of two minerals with contrasting durability (zircon and apatite) were tracked during both fluvial transport and littoral reworking. The Sefidrud river system in northern Iran, which drains the Alborz volcano-sedimentary range into the Caspian Sea, and the Sarbaz river system in southeastern Iran, which drains the Makran Accretionary Prism into the Oman Sea, were chosen for this study. To determine source rocks of the grains, and thus their nature in terms of sedimentary cycles, zircon geochronology was conducted on both rivers. The zircon data indicate that most of the Sefidrud sediments are first cycle, derived from crystalline rocks, and the Sarbaz sediments are generally recycled from older wedges of the Makran. Results from SEM analysis show significant differences between the roundness of associated zircon and apatite grains. Zircon grains remain unrounded through several cycles, while apatite grains show abrasion from the early stages of their first cycle.

This report summarizes laboratory scale studies investigating the remediation of Sr-90 by Ca-citrate-PO4 solution injection/infiltration to support field injection activities in the Hanford 100N area. This study is focused on experimentally testing whether this remediation technology can be effective under field scale conditions to mitigate Sr-90 migration 100N area sediments into the Columbia River. Sr-90 is found primarily adsorbed to sediments by ion exchange (99% adsorbed, < 1% in groundwater) in the upper portion of the unconfined aquifer and lower vadose zone. Although primarily adsorbed, Sr-90 is still considered a high mobility risk as it is mobilized by seasonal river stage increases and by plumes of higher ionic strength relative to groundwater. This remediation technology relies upon the Ca-citrate-PO4 solution forming apatite precipitate [Ca6(PO4)10(OH)2], which incorporates some Sr-90 during initial precipitation and additionally slowly incorporates Sr-90 by solid phase substitution for Ca. Sr substitution occurs because Sr-apatite is thermodynamically more stable than Ca-apatite. Once the Sr-90 is in the apatite structure, Sr-90 will decay to Y-90 (29.1 y half-life) then Zr-90 (64.1 h half-life) without the potential for migration into the Columbia River. For this technology to be effective, sufficient apatite needs to be emplaced in sediments to incorporate Sr and Sr-90 for 300 years (~10 half-lives of Sr-90), and the rate of incorporation needs to exceed the natural groundwater flux rate of Sr in the 100N area. A primary objective of this study is to supply an injection sequence to deliver sufficient apatite into subsurface sediments that minimizes initial mobility of Sr-90, which occurs because the injection solution has a higher ionic strength compared to groundwater. This can be accomplished by sequential injections of low, then high concentration injection of Ca-citrate-PO4 solutions. Assessment of low concentration Ca-citrate-PO4, citrate-PO4

Thermal histories on seven Brazilian apatites were obtained by fission track analysis using Monte Carlo simulations. The apatites were collected from two distinct geotectonic provinces. One group, originated from São Francisco craton, represents a typical cratonic domain with Proterozoic and Eopaleozoic rocks and yielded Permo-Triassic ages (counted since the instant when temperature was low enough so that the damage produced by fission tracks in apatite started to be preserved). The common thermal history accepted by all samples of this group is a linear cooling from ~90 to ~25 °C for the last 240 Ma, in agreement with present day thermal gradient and denudation rates. The other group, from Mesozoic alkaline-carbonatite complexes, in central and southeastern Brazil, yielded Cretaceous ages, close to those of the intrusions. For the samples of central Brazil, fission track analysis suggests a slow cooling from ~95 ° to ~85 °C between 90 and 60 Ma ago, followed by a faster cooling from ~85 ° to ~27 °C for the last 60 Ma. Otherwise, two trends exist for the samples of southeastern Brazil. The primary one is an increase in temperature from ~75 ° to ~95 °C, which occurred between 140 and 60 Ma ago. In this period, there is also another trend: a cooling from ~100 ° to ~80 °C. However, both trends are followed by a common thermal history during the last 60 Ma: a cooling from approximately ~80 ° to ~25 °C.

Synthesis of apatites, Na1-xKxCaPb3(PO4)3 0 ⩽ x ⩽ 1, with anion vacancy were carried out using solid state reactions. The solid solution of apatite-type structure crystallize in the hexagonal system, space group P63/m (No. 176). Rietveld refinements showed that around 90% of Pb(2+) cations are located in the (6h) sites, the left amount of Pb(2+) cations are located in the (4f) sites; 27-31% of Ca(2+) cations are located in the (6h) sites, the left amount of Ca(2+) cations are located in the (4f) sites. The ninefold coordination sites (4f) are also occupied by the K(+) and Na(+) monovalent ions. The structure can be described as built up from [PO4](3-) tetrahedra and Pb(2+)/Ca(2+) of sixfold coordination cavities (6h positions), which delimit void hexagonal tunnels running along [001]. These tunnels are connected by cations of mixed sites (4f) which are half occupied by Pb(2+)/Ca(2+) and half by Na(+)/K(+) mixed cations. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit cell group analysis and by comparison with other apatites. Vibrational spectra of all the compositions are similar and show some linear shifts of the frequencies as a function of the composition toward lower values due the substitutions of Na(+) by K(+) with a larger radius. PMID:25797224

Morphological and directional alteration of cells is essential for structurally appropriate construction of tissues and organs. In particular, osteoblast alignment is crucial for the realization of anisotropic bone tissue microstructure. In this article, the orientation of a collagen/apatite extracellular matrix (ECM) was established by controlling osteoblast alignment using a surface geometry with nanometer-sized periodicity induced by laser ablation. Laser irradiation induced self-organized periodic structures (laser-induced periodic surface structures; LIPSS) with a spatial period equal to the wavelength of the incident laser on the surface of biomedical alloys of Ti-6Al-4V and Co-Cr-Mo. Osteoblast orientation was successfully induced parallel to the grating structure. Notably, both the fibrous orientation of the secreted collagen matrix and the c-axis of the produced apatite crystals were orientated orthogonal to the cell direction. To the best of our knowledge, this is the first report demonstrating that bone tissue anisotropy is controllable, including the characteristic organization of a collagen/apatite composite orthogonal to the osteoblast orientation, by controlling the cell alignment using periodic surface geometry. PMID:25453944

The introduction of an antibiotic, sodium fusidate (SF), into the liquid phase of calcium carbonate-calcium phosphate (CaCO3-CaP) bone cement was evaluated, considering the effect of the liquid to powder ratio (L/P) on the composition and microstructure of the set cement and the injectability of the paste. In all cases, we obtained set cements composed mainly of biomimetic carbonated apatite analogous to bone mineral. With this study, we evi-denced a synergistic effect of the L/P ratio and SF presence on the injectability (i.e., the filter-pressing pheno-menon was suppressed) and the setting time of the SF-loaded cement paste compared to reference cement (without SF). In addition, the in vitro study of SF release, according to the European Pharmacopoeia recommendations, showed that, regardless of the L/P ratio, the cement allowed a sustained release of the antibiotic over 1month in sodium chloride isotonic solution at 37°C and pH7.4; this release is discussed considering the microstructure characteristics of SF-loaded cements (i.e., porosity, pore-size distribution) before and after the release test. Finally, modelling antibiotic release kinetics with several models indicated that the SF release was controlled by a diffusion mechanism. PMID:26652362

In this study chitosan/halloysite nanotube composite (CS/HNT) coatings were deposited by electrophoretic deposition (EPD) on titanium substrate. Using HNT particles were investigated as new substituents for carbon nanotubes (CNTs) in chitosan matrix coatings. The ability of chitosan as a stabilizing, charging, and blending agent for HNT particles was exploited. Furthermore, the effects of pH, electrophoretic bath, and sonicating duration were studied on the deposition of suspensions containing HNT particles. Microstructure properties of coatings showed uniform distribution of HNT particles in chitosan matrix to form smooth nanocomposite coatings. The zeta potential results revealed that at pH around 3 there is an isoelectric point for HNT and it would have cathodic and anionic states at pH values less and more than 3, respectively. Therefore, CS/HNT composite deposits were produced in the pH range of 2.5 to 3. The apatite inducing ability of chitosan-HNT composite coating assigned that HNT particles were biocompatible because they formed carbonated hydroxyapatite particles on CS/HNT coating in corrected simulated body fluid (C-SBF). Finally, electrochemical corrosion characterizations determined that corrosion resistance in CS/HNT coating has been improved compared to bare titanium substrate. PMID:26652428

Surface-mediated gene transfer systems using biocompatible calcium phosphate (CaP)-based composite layers have attracted attention as a tool for controlling cell behaviors. In the present study we aimed to demonstrate the potential of CaP-based composite layers to mediate area-specific dual gene transfer and to stimulate cells on an area-by-area basis in the same well. For this purpose we prepared two pairs of DNA–fibronectin–apatite composite (DF-Ap) layers using a pair of reporter genes and pair of differentiation factor genes. The results of the area-specific dual gene transfer successfully demonstrated that the cells cultured on a pair of DF-Ap layers that were adjacently placed in the same well showed specific gene expression patterns depending on the gene that was immobilized in theunderlying layer. Moreover, preliminary real-time PCR results indicated that multipotential C3H10T1/2 cells may have a potential to change into different types of cells depending on the differentiation factor gene that was immobilized in the underlying layer, even in the same well. Because DF-Ap layers have a potential to mediate area-specific cell stimulation on their surfaces, they could be useful in tissue engineering applications. PMID:25874757

A new oxygen isotope (δ18O) record derived from conodont apatite reveals variable long-term climate trends throughout the Triassic period. This record shows several major, first order, negative shifts reflecting intense warming episodes, not only the well-known extreme PTB-Early Triassic event (∼ 5 ‰), but also two large cycles of similar magnitude (∼1.5, ∼ 1.7 ‰) and duration (∼7 Myrs) during the late Carnian and late Norian. Between the PTB-Early Triassic and Carnian major episodes, three rapid shorter-term warming events of decreasing magnitude punctuate the mid-late Anisian, early Ladinian, and latest Ladinian, with distinct cooler (i.e. favourable) intervals characterising the early Anisian and early Carnian, indicating a fluctuating but ameliorating Middle Triassic climate trend. Two long periods of sustained cooler conditions occurred during the Late Triassic, for much of the Norian and Rhaetian. The five humid events previously recognised from the geological record, including the Carnian Pluvial Episode, are associated with the low δ18O warming phases. The magnitudes of these first order warming cycles, together with widespread geological and palaeontological evidence, suggest they were at least Tethyan-wide events.

A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 after heat treatment at 1000 °C with the preferential occupancy of Mg2+ at the crystal lattice of β-Ca3(PO4)2. The concentration of Mg2+ uptake in β-Ca3(PO4)2 is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometric value [(Ca+Mg)/P>1.67], Mg2+ precipitates as Mg(OH)2 and thereafter gets converted to MgO during heat treatment. Any kind of Mg2+ uptake in the crystal lattice of Ca10(PO4)6(OH)2 is discarded from the investigation.

Apatite fission track analysis (AFTA) has been applied to samples from four hydrocarbon well sections to study the thermal and tectonic history and the hydrocarbon prospectivity of the southern part of the Taranaki basin (New Zealand). Data from three of the wells (1 Fresne, 1 North Tasman, 1 Surville) show that the successions were exposed to higher temperatures in the past through deeper burial. Cooling from elevated paleotemperatures was effected by late Miocene uplift and erosion of 3.0 {plus minus} 0.3 km of section in 1 Fresne, {le} 2.0 {plus minus} 0.5 km in 1 Surville, and 1.0 {plus minus} 0.3 km in 1 North Tasman. In the fourth well, 1 Kupe, formations are currently at their maximum temperatures since deposition. AFTA provides unique constraints on the timing of hydrocarbon generation in relation to trap formation. The proposed source rocks in 1 Fresne passed through the oil formation window (100-150{degree}C) and into the zone of gas production (150-220{degree}C) during the middle Miocene, prior to the formation of potential trapping structures. Those in 1 North Tasman passed into the oil formation zone about the same time, and source rocks in 1 Surville have probably never been heated enough to produce oil. AFTA indicates considerable prospectivity remains in the region of 1 Kupe, where generation would have occurred after trap formation. 11 figs., 3 tabs.

Sr-substituted hydroxyapatite thin films were prepared by sputtering technique from mixture targets of hydroxyapatite (HA) and strontium apatite (SrAp). The HA and SrAp powders were mixed at 0-100% Sr/(Sr+Ca) target ratios. The coated films were recrystallized by a hydrothermal treatment to reduce film dissolution. The films were then characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP). The osteocompatiblity of the films was also evaluated by the size of the bone formation area in osteoblast cells.In the XRD patterns, peaks shifted to lower 2θ values with increasing Sr/(Sr+Ca) target ratios, which indicated Sr incorporation into the HA lattice. In the SEM observation of the hydrothermally treated films, the surface was covered with globular particles, and the size of the globular particles increased from Sr0 to Sr40, and then the size decreased from Sr60 to Sr100. The ICP analysis showed that the Sr/(Sr+Ca) film ratios were almost the same as the target ratios. In the cell culture, the bone formation area on the Sr-substituted HA films increased with increasing Sr concentration, and saturated at Sr60. PMID:24642972

The work presented details the results of an investigation into the feasibility of using Selective Laser Sintering (SLS) to directly produce customised bioceramic implants. The materials used were bioactive in nature and included a glass-ceramic and a combination of hydroxyapatite and phosphate glass. The glass-ceramic was selected from the range of apatite-mullite materials in the SiO2.Al2O3.CaO.CaF2.P2O5 series, due to their potentially suitable biological and mechanical properties. The hydroxyapatite and phosphate glass combination was chosen to allow an alternative production approach to be investigated. The viability of using both these materials with the SLS process was assessed and the process route and resulting material properties characterised using a variety of techniques including Differential Thermal Analysis (DTA), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The results obtained indicate that it was possible to produce multiple layer components from both materials using the SLS process. The glass-ceramic materials could only be processed at very low scan speeds and powers, yielding relatively brittle components. It was though possible to produce parts from the hydroxyapatite and phosphate glass combination across a much wider range of parameters, producing parts which had a greater potential for possible implant production. PMID:15965749

In situ hydroxyapatite/apatite-wollastonite glass ceramic composite was fabricated by a three dimensional printing (3DP) technique and characterized. It was found that the as-fabricated mean green strength of the composite was 1.27 MPa which was sufficient for general handling. After varying sintering temperatures (1050-1300 degrees C) and times (1-10 h), it was found that sintering at 1300 degrees C for 3 h gave the greatest flexural modulus and strength, 34.10 GPa and 76.82 MPa respectively. This was associated with a decrease in porosity and increase in densification ability of the composite resulting from liquid phase sintering. Bioactivity tested by soaking in simulated body fluid (SBF) and In Vitro toxicity studies showed that 3DP hydroxyapatite/A-W glass ceramic composite was non-toxic and bioactive. A new calcium phosphate layer was observed on the surface of the composite after soaking in SBF for only 1 day while osteoblast cells were able to attach and attain normal morphology on the surface of the composite. PMID:19225870

In this study, in order to control zinc (Zn)-release from calcium phosphate (CaP), the crystalline forms of CaP-containing Zn were modified by wet ball milling and/or heat treatment. The CaP (CaO:CaHPO4:ZnO = 7:20:3, molar ratio) was ground in a ball mill with the addition of purified water, and the ground products were heated to 400 °C and 800 °C. The physicochemical properties of these ground products were measured by powder X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy and energy-dispersive X-ray spectroscopy. Zn release characteristics from the samples were evaluated using a dissolution tester. The results of XRD and IR suggested that the structures of the starting materials were destroyed after 2.5 h of grinding, and new apatite-like amorphous solid containing Zn was generated. The Zn-release from the ground products was markedly suppressed after 2.5 h of grinding. PMID:26165245

It has been demonstrated that tropospheric molecular oxygen posses a significant isotope anomaly [1, 2 and refs. therein]. Relative to the rocks- and minerals-defined terrestrial fractionation line (TFL), tropospheric O2 has an anomaly of -0.35‰ [2]. Because almost all oxygen on Earth is contained in rocks, we suggest that the rocks- and minerals-defined TFL [3] should be used as reference when reporting isotope anomalies with ∆17O = δ'17OSMOW - βTFL δ'18OSMOW. We have developed a new technique for the determination of δ17O and δ18O of silicates by means of laser fluorination GC-CF-irmMS. We have determined βTFL to 0.5247 (N > 100), which is identical to the value reported by other laboratories and techniques [2, 3]. The uncertainty in ∆17O is ±0.03 (1σ) for a single analysis. It was suggested that ∆17O of tropospheric O2 can be used as proxy for the global bioactivity rate [GBR, 1] as well as for past atmospheric CO2 concentrations [4]. Past ∆17O of tropospheric O2 can be determined by analyzing O2 trapped in ice [1, 5] or by analyzing sulfates from terrestrial sulphide oxidation [4]. Disadvantage of ice core data is the limitation in time back <1 Myrs. The sulfate approach is used to trace ∆17O of air O2 back to Proterozoic times. Disadvantage of this technique is the uncertainty in the proportion of oxygen from O2 and oxygen from ambient water during oxidation of the sulphides. We suggest that oxygen from tooth and bone phosphate can be used as proxy for the ∆17O of air O2. Mass balance calculations [e.g. 6] suggest that a considerable portion of oxygen in biogenic apatite sources from respired air O2. We have analyzed tooth (enamel, dentine) and bone material by means of direct fluorination for their δ17O and δ18O. We have chosen material of mammals of different body mass (Mb) from Northern Germany (except Indian Elephant). The ∆17O of apatite varies between -0.16‰ for a wood mouse (Apodemus sylvaticus) and +0.04‰ for a wild boar

Recent work suggests a link between third-order (~1-5 Myr) sea-level fluctuations and climate change, even in greenhouse periods. Upper Ordovician third-order transgressive-regressive sequences are pervasive in the stratigraphic record, can be correlated worldwide (i.e. North America, Baltica, China), and ambiguous in cause. We are evaluating climate's role in third-order sea-level change by analyzing the δ18O of conodont apatite, which is a proxy for both glacio-eustasy and paleotemperature. Conodont phosphatic oxygen is a more robust repository of primary oxygen isotope values than more extensively-studied calcareous fossils, which have been extensively studied. If sea-level change is climatically-driven (glacio-eustasy and thermo-eustasy), δ18O values will decrease with sea-level rise and increase with sea-level fall. We report preliminary results from Upper Ordovician sequences in the Monitor Range of central Nevada. The six stratigraphic sequences (30m-95m thick) preserve basinal-to-outer-shelf carbonates with the youngest sequence representing the Hirnantian glaciation. We collected conodont samples at a 2-10m resolution and also determined bulk carbonate δ13C for additional chemostratigraphy. With this information, we hope to determine if glacio-eustasy has a role within the five pre-Hirnantian sequences.

Titanium alloy beta 21S with composition Ti-15Mo-3Nb-3Al-0.2Si was plasma nitrided using inductively coupled RF Plasma with 100% N2 and 80% N2-20% H2 at 800 °C for 4 h. XRD and micro Raman studies show the formation of titanium nitrides. Potentiodynamic polarization studies in Hank's solution show the corrosion resistance of the 80-20% (N2-H2) treated samples to be better than the 100% N2 treated samples. However, untreated samples show better corrosion resistance than the treated samples. Electrochemical impedance spectroscopy (EIS) studies show higher charge transfer resistance and lower double layer capacitance for the substrate compared to the nitrided samples. FESEM images of samples immersed in SBF show that growth of apatite is more and the size of deposits are larger on nitrided samples, especially on those nitrided with hydrogen dilution, as compared to that on the untreated substrate. EDS results show a decrease in nitrogen content and increase in oxygen content after corrosion experiments. XPS spectra from the nitrided and corrosion tested samples show the presence of oxide, nitride and oxynitride on the surface and after corrosion studies the samples are covered with oxide. Nitrided samples immersed in Hank's solution for one day show higher amount of calcium, phosphorous and oxygen in hydroxide form than the substrate.

Experimental degassing of H-, F-, Cl-, C-, and S-bearing species from volatile-bearing magma of lunar composition at low P and fO2 close to quartz-iron-fayalite indicates that the composition of the fluid/vapor phase that is lost changes over time. A highly H-rich vapor phase is exsolved within the first 10 min. of degassing leaving behind a melt that is effectively dehydrated. Some Cl, F, and S is also lost during this time, presumably as HCl, HF, and H2S gaseous species; however much of the original inventory of Cl, F, and S components are retained in the melt. After 10 min., the exsolved vapor is dry and dominated by S- and halogen-bearing phases, presumably consisting of metal halides and sulfides, which evolves over time towards F enrichment. This vapor evolution provides important constraints on the geochemistry of volatile-bearing lunar phases that form subsequent to or during degassing. The rapidity of H loss suggests that little if any OH-bearing apatite will crystallize from surface or near surface (≈7m) melts and that degassing of lunar magmas will cause the compositions of apatites to evolve first towards the F-Cl apatite binary and eventually towards end member fluorapatite during crystallization. During the stage of loss of primarily H component from the melt, Cl would have been lost primarily as HCl, which is reported not to fractionate Cl isotopes at magmatic temperatures. After the loss of H-bearing species, continued loss of Cl would result in the degassing of metal chlorides, as a mechanism to fractionate Cl isotopes. After the onset of metal chloride degassing, the δ37Cl of the melt would increase to +6 (82% Cl loss), +8 (85% Cl loss), and +20‰ (95% Cl loss) at 1, 4, and 6 hours, respectively, approximated in a computed trajectory of δ37Cl values in basalt during degassing of FeCl2. This strong enrichment of 37Cl in the melt after metal chloride volatilization is fully consistent with values measured for the non-leachates of a variety of

To understand the evolution of the passive continental margin in Argentina apatite fission track dating is an appropriate method, which will lead to new conclusions in this area. The Tandilia System, also called Sierras Septentrionales, is located south of the Río de la Plato Craton in eastern Argentina in the state of Buenos Aires. North of the hills Salado basin is orientated whereas the Claromeó basin is located south of the mountain range. In contrary to most basins along the southamerican passive continental margin the Tandilia-System and the neighbouring basins trend perpendicular to the coast line. The topography ranges between 50 and 250m within the study area and is therefore fairly flat. The igneous-metamorphic basement is pre-proterozoic in age build up of mainly granitic-tonalitic gneisses, migmatites, amphibolites, some ultramafic rocks and granitoid plutons and is overlain by a series of Neoproterozoic to early Paleozoic sediments (Cingolani, 2010). The aim of the study is to evaluate the long-term landscape evolution of the passive continental margin in eastern Argentina in terms of thermal history and exhumation. For that purpose samples were taken from the Sierra Septentrionales basement analyzed for the apatite-FT method. The results so far indicate apatite fission track ages between 146.2 (10.1) Ma and 200.4 (12.7) Ma, which shows all samples have been reseted. Still ongoing length measurements will lead to 2D thermo kinematic Hefty (Ketcham, 2005; Ketcham et al., 2009; Ketcham, 2007) models. This will leads to further more insights on the cooling history and tectonic activities in the research area. References: Cingolani C. A. (2010): The Tandilia System of Argentina as a southern extension of the Río de la Plata craton: an overview. Int. J. Earth Sci. (Geol. Rundsch.) (2011) 100:221-242, doi 10.1007/s00531-010-0611-5. Ketcham, R. A. (2005): Forward and inverse modeling of low-temperature thermochronometry data, in Low

The in-situ Sr isotopic systematics of scheelite and apatite from the Felbertal W deposit and a few regional Variscan orthogneisses ("Zentralgneise") have been determined by LA-MC-ICP-MS. The 87Sr/86Sr ratios of scheelite and apatite from the deposit are highly radiogenic and remarkably scattering. In the early magmatic-hydrothermal scheelite generations (Scheelite 1 and 2) the 87Sr/86Sr ratios range from 0.72078 to 0.76417 and from 0.70724 to 0.76832, respectively. Metamorphic Scheelite 3, formed by recrystallisation and local mobilisation of older scheelite, is characterised by even higher 87Sr/86Sr values between 0.74331 and 0.80689. Statistics allows discriminating the three scheelite generations although there is considerable overlap between Scheelite 1 and 2; they could be mixtures of the same isotopic reservoirs. The heterogeneous and scattering 87Sr/86Sr ratios of the two primary scheelite generations suggest modification of the Sr isotope system due to fluid-rock interaction and isotopic disequilibrium. Incongruent release of 87Sr from micas in the Early Palaeozoic host rocks of the Habach Complex contributed to the solute budget of the hydrothermal fluids and may explain the radiogenic Sr isotope signature of scheelite. Spatially resolved analyses revealed isotopic disequilibrium even on a sub-mm scale within zoned Scheelite 2 crystals indicating scheelite growth in an isotopic dynamical hydrothermal system. Zoned apatite from the W mineralised Early Carboniferous K1-K3 orthogneiss in the western ore field yielded 87Sr/86Sr of 0.72044-0.74514 for the cores and 0.74535-0.77937 for the rims. Values of magmatic apatite cores from the K1-K3 orthogneiss are comparable to those of primary Scheelite 1; they are too radiogenic to be magmatic. The Sr isotopic composition of apatite cores was therefore equally modified during the hydrothermal mineralisation processes, therefore supporting the single-stage genetic model in which W mineralisation is associated with

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has

The Antioqueño plateau (AP), in the northernmost Cordillera Central, Colombia, is the most extensive and best preserved relict surface in the Northern Andes. Apatite (U-Th)/He (AHe) and fission track (AFT) results from twenty two samples, collected from paleocrustal depths along two vertical profiles in canyons dissecting the AP, constrain Cenozoic erosional exhumation of this segment of the Andean range. The two profiles exhibit excellent reproducibility of AHe and AFT data. Helium ages increase with elevation from ~22-49 Ma. A marked inflection point in the AHe age-elevation plots at 25 Ma defines the bottom of the post-Oligocene He partial retention zone (PRZ). Virtually invariant ages at ~25 Ma record onset of rapid exhumation in the AP. A more subtle slope change in the PRZ at ~43 Ma is interpreted as a minor exhumation pulse. AFT better defines timing and intensity of Eocene exhumation. AFT ages for both profiles vary from ~30-49 Ma and are consistently older than AHe ages. AFT data display invariant ages (±2σ) between 1500-2400 m elevations while confined track length data exhibit uni-modal distributions with a mean track length of ~14.2 μm. Both facts indicate rapid cooling. This is further supported by virtually concordant AFT and AHe ages for both profiles between 1500 to 2200 m implying that rocks were exhumed from temperatures >120°C to below AHe closure temperature 60°C. Assuming a geothermal gradient of ~25°C/km this corresponds to exhumation rates in the order of 0.5 mm/y, comparable in intensity to the Miocene pulse defined by AHe. Integrated thermal modeling show an episode of rapid cooling at ~43-49 Ma. AFT profiles show an apparent inflection point at ~1400 m, which defines the upper boundary of an apatite partial annealing zone (PAZ) exhumed during the 43-49 Ma cooling event. The position of the PAZ and PRZ relative to the present erosional surface point to average erosion rates of ~0.03 mm/yr, which constitute very low denudation rates

We present new apatite fission-track analysis (AFTA) data from 27 basement samples from Norway south of ~60°N. The data define three events of cooling and exhumation that overlap in time with events defined from AFTA in southern Sweden (Japsen et al. 2015). The samples cooled below palaeotemperatures of >100°C in a major episode of Triassic cooling as also reported by previous studies (Rohrman et al. 1995). Our study area is just south of the Hardangervidda where Cambrian sediments and Caledonian nappes are present. We thus infer that these palaeotemperatures reflect heating below a cover that accumulated during the Palaeozoic and Triassic. By Late Triassic, this cover had been removed from the Utsira High, off SW Norway, resulting in deep weathering of a granitic landscape (Fredin et al. 2014). Our samples were therefore at or close to the surface at this time. Palaeotemperatures reached ~80°C prior to a second phase of cooling and exhumation in the Jurassic, following a phase of Late Triassic - Jurassic burial. Upper Jurassic sandstones rest on basement near Bergen, NW of our study area (Fossen et al. 1997), and we infer that the Jurassic event led to complete removal of any remaining Phanerozoic cover in the region adjacent to the evolving rift system prior to Late Jurassic subsidence and burial. The data reveal a third phase of cooling in the early Miocene when samples that are now near sea level cooled below palaeotemperatures of ~60°C. For likely values of the palaeogeothermal gradient, such palaeotemperatures correspond to burial below rock columns that reach well above the present-day landscape where elevations rarely exceed 1 km above sea level. This implies that the present-day landscape was shaped by Neogene erosion. This is in agreement with the suggestion of Lidmar-Bergström et al. (2013) that the near-horizontal Palaeic surfaces of southern Norway are the result of Cenozoic erosion to sea level followed by uplift to their present elevations in a

The Meishan deposit (338 Mt at 39 % Fe) comprises massive ores in the main orebody and stockwork and disseminated ores along the main orebody. Four stages of mineralization and related alteration have been identified. The second stage of mineralization, which was the main stage of iron mineralization, formed stringer, disseminated iron ores, as well as the main Meishan orebody. The fourth stage formed small pyrite and/or gold orebodies above or alongside the main magnetite orebody. Stage 2 apatites have homogenization temperatures of 257-485 °C and salinities of 7.3-11 wt% NaCleq. Calculated δ18Ofluid values of magnetite and apatite from the disseminated ores vary between 7.7 and 14.9 ‰, which is similar to values observed in the massive ores (8.1-12.9 ‰). The high-18O fluids at Meishan have been interpreted as being of magmatic-hydrothermal origin. These fluids are indicative of the boiling of ore-forming fluids. Quartz, occurring as cavity fillings, gives homogenization temperatures from 202 to 344 °C, with most values lying between 250 and 330 °C. Corresponding salinities are ˜5 wt% NaCleq. Calculated δ18Ofluid values are +6.4 to +6.8 ‰. These values indicate that the lower-temperature (250-330 °C) quartz was deposited from a cooling magmatic-hydrothermal fluid. Stage 3 siderites contain fluid inclusions that homogenized between 190 and 310 °C, mainly between 210 and 290 °C. Corresponding salinities are 4-8 wt% NaCleq. Stage 4 quartz-carbonate veinlets contain fluid inclusions that homogenized at moderate to low temperatures (150-230 °C) and exhibit low salinities (2-10 wt% NaCl eq). δ18Ofluid values of the mineralizing fluids for the quartz and calcite can be calculated to vary from -0.7 to +5.6 ‰ and +6.3 to +10.2 ‰, respectively. While there is some overlap, the δ18O values of the fluids are generally lower than those observed in the massive and disseminated magnetite ores. δD values for the quartz and calcite vary between -154 and -123

The effects of a biphasic mineralized collagen scaffold (BCS) containing intrafibrillar silica and apatite on osteogenesis of mouse mesenchymal stem cells (mMSCs) and inhibition of receptor activator of nuclear factor κB ligand (RANKL)-mediated osteoclastogenesis were investigated in the present study. mMSCs were cultured by exposing to BCS for 7 days for cell proliferation/viability examination, and stimulated to differentiate in osteogenic medium for 7–21 days for evaluation of alkaline phosphatase activity, secretion of osteogenic deposits and expression of osteoblast lineage-specific phenotypic markers. The effect of BCS-conditioned mMSCs on osteoclastogenesis of RAW 264.7 cells was evaluated by tartrate-resistant acid phosphatase staining and resorption pit analysis. The contributions of mitogen-activated protein kinase (MAPK) and phosphatidylinositol-3 kinase (PI3K) signal transduction pathways to osteogenesis of mMSCs and their osteoprotegerin (OPG) and RANKL expressions were also evaluated. Compared with unmineralized, intrafibrillarly-silicified or intrafibrillarly-calcified collagen scaffolds, BCS enhanced osteogenic differentiation of mMSCs by activation of the extracellular signal regulated kinases (ERK)/MAPK and p38/MAPK signaling pathways. After mMSCs were exposed to BCS, they up-regulated OPG expression and down-regulated RANKL expression through activation of the p38/MAPK and PI3K/ protein kinase B (Akt) pathways, resulting in inhibition of the differentiation of RAW 264.7 cells into multinucleated osteoclasts and reduction in osteoclast function. These observations collectively suggest that BCS has the potential to be used in bone tissue engineering when the demand for anabolic activities is higher than catabolic metabolism during the initial stage of wound rehabilitation. PMID:25792280

Highlights: Black-Right-Pointing-Pointer To develop effective vaccine, we examined the effects of CO{sub 3}Ap as an antigen carrier. Black-Right-Pointing-Pointer OVA contained in CO{sub 3}Ap was taken up by BMDCs more effectively than free OVA. Black-Right-Pointing-Pointer OVA-immunized splenocytes was activated by OVA contained in CO{sub 3}Ap effectively. Black-Right-Pointing-Pointer OVA contained in CO{sub 3}Ap induced strong OVA-specific immune responses to C57BL/6 mice. Black-Right-Pointing-Pointer CO{sub 3}Ap is promising antigen carrier for the achievement of effective vaccine. -- Abstract: The ability of carbonate apatite (CO{sub 3}Ap) to enhance antigen-specific immunity was examined in vitro and in vivo to investigate its utility as a vaccine carrier. Murine bone marrow-derived dendritic cells took up ovalbumin (OVA) containing CO{sub 3}Ap more effectively than free OVA. Interestingly, mice immunized with OVA-containing CO{sub 3}Ap produced OVA-specific antibodies more effectively than mice immunized with free OVA. Furthermore, immunization of C57BL/6 mice with OVA-containing CO{sub 3}Ap induced the proliferation and antigen-specific production of IFN-{gamma} by splenocytes more strongly than immunization with free OVA. Moreover, no significant differences were detected in the induction of delayed-type hypersensitivity responses, an immune reaction involving an antigen-specific, cell-mediated immune response between OVA-containing CO{sub 3}Ap and OVA-containing alumina salt (Alum), suggesting that CO{sub 3}Ap induced cell-mediated immune response to the same degree as Alum, which is commonly used for clinical applications. This study is the first to demonstrate the induction of antigen-specific immune responses in vivo by CO{sub 3}Ap.

Dead Sea rift (DSR), developed along the Dead Sea transform plate boundary, is characterized by salient flanks and morphotectonic asymmetry. Apatite fission track thermochronology (AFT) along ~1200 m high vertical profiles in Neoproterozoic basement and overlying Cambrian sandstone in southwestern Jordan is used to reconstruct timing, magnitude, and rate of uplift and denudation of the eastern DSR flank and examine its relationship to rift development and its flank landscape. Time-temperature models based on AFT data suggest three major Phanerozoic heating and cooling episodes, Late Paleozoic, Early Cretaceous, and Oligocene. The latest episode, on which this study focuses, indicates uplift of ~3.8±0.3 km under a moderate paleogeothermal gradient. About 40% of the uplift was tectonically driven with the remainder attributed to isostatic rebound in response to denudation and erosion. Models suggest that uplift commenced in the Oligocene with a considerable part occurring prior to development of the DSR, despite being ~200 km from the Red Sea-Gulf of Suez rift margin. Uplift is probably part of a regional rearrangement along the western Arabian platform margin occurring at the time of Red Sea rift initiation. Transition from primarily sedimentary layer stripping, most likely by scarp retreat, to one of dominantly incision of the underlying crystalline basement occurred in Late Miocene-Pliocene time following enhanced subsidence and development of a low base level in the DSR. Consequently, the magnitude of uplift by isostatic rebound due to incision exceeded lowering by surface truncation and increased summit elevation and riftward flexing of the flank.

During the cold Late Barremian-Early Albian interval, terrestrial environments in East Asia were populated by rich and diverse vertebrate faunas characterized by a strong provincialism. The latitudinal gradient of temperature and the existence of geographic barriers likely accounted for some aspects of this heterogeneous distribution of faunas. Other factors, however, such as local environmental conditions and interactions within vertebrate communities, which could have influenced their distribution, have not yet been fully identified and understood. Therefore, new and published oxygen and carbon isotope compositions of apatite from Chinese and Thai reptiles (dinosaurs, crocodilians and turtles) have been analyzed and interpreted in terms of ecology, local air temperature and precipitation amounts. Differences in carbon and oxygen isotope compositions between various groups of sympatric plant-eating dinosaurs (sauropods, ornithopods and ceratopsians) indicate food resources partitioning among them most likely to avoid competition. Mid-latitude environments, where the Jehol Biota flourished, were submitted to cool temperate climatic conditions with Mean Air Temperature (MAT) of 10 ± 4 °C and Mean Annual Precipitations (MAP) of about 600 mm/yr compatible with the existence of forest environments. By contrast, sub-tropical regions, characterized by MAT of about 20-25 °C were either submitted to high amounts of seasonal precipitations (of about 1200 mm/yr in Thailand) or to significant aridity (MAP of about 400 mm/yr in South China). This difference in precipitation regime between Thailand and South China may be attributed to the occurrence of the Coastal Cordillera extending along the East margin of the South China block. These mountain ranges likely prevented humid air masses from the Pacific to penetrate some parts of South China, thus generating a "rain shadow effect". Mosaic environments characterizing East Asia during the Late Early Cretaceous may have acted

The Kyrgyz Range, the northernmost portion of the Kyrgyzstan Tien Shan, displays topographic evidence for lateral propagation of surface uplift and exhumation. The highest and most deeply dissected segment lies in the center of the range. To the east, topography and relief decrease, and preserved remnants of a Cretaceous regional erosion surface imply minimal amounts of bedrock exhumation. The timing of exhumation of range segments defines the lateral propagation rate of the range-bounding reverse fault and quantifies the time and erosion depth needed to transform a mountain range from a juvenile to a mature morphology. New apatite fission-track (AFT) data from three transects from the eastern Kyrgyz Range, combined with published AFT data, demonstrate that the range has propagated over 110 km eastwards over the last 7-11 Myr. Based on the thermal and topographic evolutionary history, we present a model for a time-varying exhumation rate driven by rock uplift and changes in erodability and the time scale of geomorphic adjustment to surface uplift. Easily eroded, Cenozoic sedimentary rocks overlying resistant basement control early, rapid exhumation and slow surface upliftrates. As increasing amounts of resistant basement are exposed, exhumation rates decrease while surface uplift rates are sustained or increase, thereby growing topography. As the range becomes high enough to cause ice accumulation and develop steep river valleys, fluvial and glacial erosion become more powerful and exhumation rates once again increase. Independently determined range-noma1 shortening rates have also varied over time, suggesting a feedback between erosional efficiency and shortening rate.

The northeastern Pamir is a key location to explore Asian intracontinental tectonic processes during the Cenozoic. New zircon fission-track (ZFT) data show a 20- to 50-km-wide region of partially reset ages on the northeastern margin of the Pamir salient, interpreted as an exhumed and tilted partial annealing zone (PAZ). Widespread ZFT age peaks at ~ 50 Ma within the ZFT PAZ likely date early motion of the Kashgar-Yecheng transfer system (KYTS), but suggest this fault system was narrower in the Early Cenozoic than it is today. Apatite fission-track (AFT) ages of ~ 10-6 Ma, combined with field observations across the KYTS, hint at an episode of strong thrusting-related exhumational cooling, which indicates that the modern fault system probably formed at this time. To the southwest of the KYTS, the combination of new fission-track and existing thermochronology data allows establishing temperature-time trajectories that present diachronous rapid cooling from ~ 450 to 120 °C in the Sares (> 13-10 Ma), Muztagata (~ 10-7 Ma) and Kongur Shan (~ 3-1 Ma) domes. Rapid cooling in the eastern Sares and southern Muztagata massifs is driven by doming, as supported by kinematic analyses of the Shen-ti fault. Successive rapid cooling of these massifs confirms eastward propagation of doming processes, shortly postdating magma emplacement at ~ 11 Ma. We propose that the synchronicity of regional tectonism, magmatism and metamorphism implies that strong crustal thickening and contraction occurred beneath the northeastern Pamir during the Middle-Late Miocene, possibly associated with initial collision between the Pamir and Tian Shan.

Addition of common dietary carbohydrates to Millipore-treated human whole saliva either enhances or inhibits the formation of salivary precipitates, some carbohydrates showing no effect. The purpose of this study was to investigate the precipitation conditions more thoroughly and to elucidate the chemical nature of the precipitates formed. D-Xylose either enhanced precipitation (in long-term incubations) or had no appreciable effect (in 10 minute incubations). Other aldo- and keto-sugars and disaccharides (maltose, sucrose, lactose) generally enhanced precipitation, whereas all polyols (xylitol, D-sorbitol, mannitol, and maltitol) retarded the formation of turbidity in saliva. Xylitol inhibited formation of precipitates also in the presence of D-xylose, dextrans, and starch. Fast protein liquid chromatography (FPLC) of EDTA-soluble pellets obtained by centrifugation of the precipitates produced two major protein fractions (I and II) with a molecular weight of 112,000 and 46,000, respectively. The carbohydrates exerted a selective effect on the relative size of I and II in that polyol incubations resulted in a I to II ratio of 1:3, whereas control incubations (without added sugars) and incubations with other carbohydrates gave ratios of 1:6 to 1:10. Both peaks contained large amounts of acidic amino acids, proline, and glycine. The saliva precipitates contained a substantial portion of a crystalline phase that had the crystal structure of apatite, the individual crystallites being extremely small (less than 1 micron) with a Ca:P ratio of 1.46. The carbohydrates had a similar effect on the overall inorganic composition of the precipitates, but they had a clearly selective effect on the rate of formation of precipitates and on the relative amount of coprecipitating salivary proteins. This selectivity indicates that these carbohydrates, when consumed habitually, may exert different effects on the precipitation of Ca-salts at mineral-deficient enamel and dentine sites

Despite decades of study, the timing, rates, and magnitude of extension in the Basin and Range are poorly quantified in some areas. This study integrates new zircon and apatite (U-Th)/He analyses (ZrnHe and ApHe) with published thermochronologic data to quantify these extensional parameters in the Southern Snake Range (SSR) of east-central Nevada. The new ZrnHe dates range from 40.7 ± 4.9 Ma in the western SSR to 21.0 ± 3.3 Ma near the present-day trace of the Southern Snake Range Décollement (SSRD), and the ApHe dates range from 15.1 ± 2.4 Ma in the central SSR to 13.6 ± 0.7 Ma closest to the SSRD trace. These new and previously published low-temperature thermochronologic cooling ages were inverted for the extensional history of the SSR using a Bayesian Monte Carlo method incorporating Pecube. The posterior extensional histories indicate three significant pulses of extension occurred during the Paleogene and Neogene: (1) ~50-45 to ~38 Ma (Eocene), (2) ~33-30 to ~23 Ma (Oligocene), and (3) ~23-20 to ~10-8 Ma (Miocene). Modeled rates of extension were low at ≤ 0.5 mm a-1; however, more rapid rates possibly occurred during the Eocene and the Miocene based on posterior histories. Net cumulative extension from posterior histories is 19.8 to 34.9 km, with a mean of 29.7 km. About 10-18 km of extension occurred during the Eocene and Oligocene. Model results indicate no relationship between extension and magmatism in the SSR. Our new model results and interpretations also indicate extensional collapse of the Nevadaplano initiated prior to ~17 Ma.

We present an apatite fission-track (AFT) study of five plutonic rocks and seven metamorphic rocks across 310 km of the Yukon-Tanana Upland in east-central Alaska. Samples yielding ???40 Ma AFT ages and mean confined track lengths > 14 ??m with low standard deviations cooled rapidly from >120??C to 40 Ma suggest partial annealing and, therefore, lower maximum temperatures (???90-105??C). A few samples with single-grain ages of ???20 Ma apparently remained above ???50??C after initial cooling. Although the present geothermal gradient in the western Yukon-Tanana Upland is ???32??C/km, it could have been as high as 45??C/km during a widespread Eocene intraplate magmatic episode. Prior to rapid exhumation, samples with ???40 Ma AFT ages were >3.8-2.7 km deep and samples with >50 Ma AFT ages were >3.3-2.0 km deep. We calculate a 440-320 m/Ma minimum rate for exhumation of all samples during rapid cooling. Our AFT data, and data from rocks north of Fairbanks and from the Eielson deep test hole, indicate up to 3 km of post-40 Ma vertical displacement along known and inferred northeast-trending high-angle faults. The predominance of 40-50 Ma AFT ages throughout the Yukon-Tanana Upland indicates that, prior to the post-40 Ma relative uplift along some northeast-trending faults, rapid regional cooling and exhumation closely followed the Eocene extensional magmatism. We propose that Eocene magmatism and exhumation were somehow related to plate movements that produced regional-scale oroclinal rotation, northward translation of outboard terranes, major dextral strike-slip faulting, and subduction of an oceanic spreading ridge along the southern margin of Alaska.

The low-temperature thermochronology has been an important tool to quantify geological process in passive continental margins. In this context, the Angolan margin shows evidence of a polycyclic post-rift evolution marked by different events of uplift, basin inversion and changes in sedimentation rates to the marginal basins, which have controlled the salt tectonics and the hydrocarbon deposits (1,2,3,4). To understand the post break-up evolution of the southwestern Angola margin, it were collected outcrop samples for apatite fission track (AFT) and (U-Th)/He analysis ranging in elevation from 79 m to 1675 m from the coast toward the interior plateau in a profile between Namibe and Lubango cities. The area lies on the edge of Central and Southern Atlantic segments a few kilometers northward the Walvis ridge and encompasses the Archean and Proterozoic basement rocks of the Congo craton. The AFT ages ranging from 120.6 ± 8.9 Ma to 328.8 ± 28.5 Ma and they show a trend of increasing age toward the Great Escarpment with some exceptions. The partial mean track lengths (MTLs) vary between 11.77 ± 1.82 μm to 12.34 ± 1.13 μm with unimodal track length distributions (TDLs). The partial (U-Th)/He ages ranging from 104.85 ± 3.15 Ma to 146.95 ± 4.41 Ma and show the same trend of increasing ages landward, little younger than the AFT ages, which could be interpreted as a fast exhumation episode in Late Jurassic - Early Cretaceous times. The thermal histories modelling has been constrained with the kinetic parameters Dpar (5) and c-axis angle (6) by the software Hefty (7). Both AFT and (U-Th)/He thermal histories modelling indicate three episodes of denudation/uplift driven cooling: (a) from Late Jurassic to Early Cretaceous, (b) a smallest one in the Late Cretaceous and (c) from Oligocene-Miocene to recent, which are compatible with geophysical data of the offshore Namibe basin that estimate the greater thickness of sediments formed in the first and third episodes

Apatite is a ubiquitous accessory mineral in a variety of rocks and hydrothermal ores. Strontium isotopes of apatite are well known to retain petrogenetic information and have been widely used to investigate the origin of igneous rocks, but such attempts have rarely been made to constrain ore-forming processes of hydrothermal systems. We here report in situ LA-MC-ICPMS Sr isotope data of apatite from the ~1660-Ma Yinachang Fe-Cu-REE deposit, Southwest China. The formation of this deposit was coeval to the emplacement of regionally distributed doleritic intrusions within a continental-rift setting. The deposit has a paragenetic sequence consisting of sodic alteration (stage I), magnetite mineralization (stage II), Cu sulfide and REE mineralization (stage III), and final barren calcite veining (stage IV). The stage II and III assemblages contain abundant apatite, allowing to investigate the temporal evolution of the Sr isotopic composition of the ore fluids. Apatite of stage II (Apt II) is associated with fluorite, magnetite, and siderite, whereas apatite from stage III (Apt III) occurs intimately intergrown with ankerite and Cu sulfides. Apt II has 87Sr/86Sr ratios varying from 0.70377 to 0.71074, broadly compatible with the coeval doleritic intrusions (0.70592 to 0.70692), indicating that ore-forming fluids responsible for stage II magnetite mineralization were largely equilibrated with mantle-derived mafic rocks. In contrast, Apt III has distinctly higher 87Sr/86Sr ratios from 0.71021 to 0.72114, which are interpreted to reflect external radiogenic Sr, likely derived from the Paleoproterozoic strata. Some Apt III crystals have undergone extensive metasomatism indicated by abundant monazite inclusions. The metasomatized apatite has much higher 87Sr/86Sr ratios up to 0.73721, which is consistent with bulk-rock Rb-Sr isotope analyses of Cu ores with 87Sr/86Sri from 0.71906 to 0.74632. The elevated 87Sr/86Sr values of metasomatized apatite and bulk Cu ores indicate

To improve the bioactivity and cytocompatibility of biomedical titanium dioxide coating, many efforts have been made to modify its surface composition and topography. Meanwhile, CaSiO(3) was commonly investigated as coating material on titanium implants for fast fixation and firm implant-bone attachment due to its demonstrated bioactivity and osteointegration. In this work, gradient TiO(2)/CaSiO(3) coating on titanium was prepared by a two-step procedure, in which porous and nanostructured TiO(2) coating on titanium was prepared by plasma electrolytic oxidation in advance, and then needle and flake-like CaSiO(3) nanocrystals were deposited on the TiO(2) coating surface by electron beam evaporation. In view of the potential clinical applications, apatite-forming ability of the TiO(2)/CaSiO(3) coating was evaluated by simulated body fluid (SBF) immersion tests, and MG63 cells were cultured on the surface of the coating to investigate its cytocompatibility. The results show that deposition of CaSiO(3) significantly enhanced the apatite-forming ability of nanostructured TiO(2) coating in SBF. Meanwhile, the MG63 cells on TiO(2)/CaSiO(3) coating show higher proliferation rate and vitality than that on TiO(2) coating. In conclusion, the porous and nanostructured TiO(2)/CaSiO(3) coating on titanium substrate with good apatite-forming ability and cytocompatibility is a potential candidate for bone tissue engineering and implant coating. PMID:22796775

In this study, to provide porous anodic alumina (PAA) with bioactivity and anti-bacterial properties, sol-gel derived bioactive CaO-SiO2-Ag2O materials were loaded onto and into PAA nano-pores (termed CaO-SiO2-Ag2O/PAA) by a sol-dipping method and subsequent calcination of the gel-glasses. The in vitro apatite-forming ability of the CaO-SiO2-Ag2O/PAA specimens was evaluated by soaking them in simulated body fluid (SBF). The surface microstructure and chemical property before and after soaking in SBF were characterized. Release of ions into the SBF was also measured. In addition, the antibacterial properties of the samples were tested against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The results showed that CaO-SiO2-Ag2O bioactive materials were successfully decorated onto and into PAA nano-pores. In vitro SBF experiments revealed that the CaO-SiO2-Ag2O/PAA specimens dramatically enhanced the apatite-forming ability of PAA in SBF and Ca, Si and Ag ions were released from the samples in a sustained and slow manner. Importantly, E. coli and S. aureus were both killed on the CaO-SiO2-Ag2O/PAA (by 100%) samples compared to PAA controls after 3 days of culture. In summary, this study demonstrated that the CaO-SiO2-Ag2O/PAA samples possess good apatite-forming ability and high antibacterial activity causing it to be a promising bioactive coating candidate for implant materials for orthopedic applications. PMID:26478362

Phosphorus (P) availability varies considerably throughout Taylor Valley, Antarctica. As an essential nutrient, P content and weathering have significant implications for the diversity and functioning of biota in soils, streams, and lakes. In upper Taylor Valley (Bonney Basin), soils have much lower total P content than in lower Taylor Valley (Fryxell Basin), 0.4 versus 1.5 g/kg soil. We hypothesize that this striking contrast is related to differences in glacial drift source and weathering rates. We investigated the primary source of mineral P (apatite) and the grain-scale weathering processes resulting in the release of P into streams and adjacent soils in the Bonney and Fryxell Basins. Physical erosion, chemical weathering, and biological weathering all leave distinctive patterns on the surface of individual apatite grains. By inspecting these surfaces, we determined the relative importance of weathering processes for P cycling. Apatite grains were separated from loose glacial drift using heavy-liquid and magnetic techniques. Individual grains were analyzed using SEM-EDS. We observe significant differences between the grains collected from the two basins. Grains from the Bonney Basin are more elongated and have a higher proportion of crystal faces. These results suggest that rates of physical weathering have been lower in the Bonney Basin than in the Fryxell Basin. In addition, we will present results on grain surface morphologies, indicative of chemical and biological weathering. As the climate warms, more liquid water is expected to be available within the Taylor Valley system. This increase in water will likely lead to higher rates of P weathering, potentially altering nutrient limitation in this environment. Understanding how the P cycle will respond to a changing climate is contingent on understanding the current weathering processes and controls on P availability.

Pure titanium substrates were chemically oxidized with H2O2 and subsequent thermally oxidized at 400 °C in air to form anatase-type titania layer on their surface. The chemically and thermally oxidized titanium substrate (CHT) was aligned parallel to the counter specimen such as commercially pure titanium (cpTi), titanium alloy (Ti6Al4V) popularly used as implant materials or Al substrate with 0.3-mm gap. Then, they were soaked in Kokubo's simulated body fluid (SBF, pH 7.4, 36.5 °C) for 7 days. XRD and SEM analysis showed that the in vitro apatite-forming ability of the contact surface of the CHT specimen decreased in the order: cpTi > Ti6Al4V > Al. EDX and XPS surface analysis showed that aluminum species were present on the contact surface of the CHT specimen aligned parallel to the counter specimen such as Ti6Al4V and Al. This result indicated that Ti6Al4V or Al specimens released the aluminum species into the SBF under the spatial gap. The released aluminum species might be positively or negatively charged in the SBF and thus can interact with calcium or phosphate species as well as titania layer, causing the suppression of the primary heterogeneous nucleation and growth of apatite on the contact surface of the CHT specimen under the spatial gap. The diffusion and adsorption of aluminum species derived from the half-sized counter specimen under the spatial gap resulted in two dimensionally area-selective deposition of apatite particles on the contact surfaces of the CHT specimen. PMID:25989935

This study presents a facile synthesis of biomimetic hydroxyapatite nanorod/poly(D,L) lactic acid (HAp/PDLLA) scaffolds with the use of solvent casting combined with a salt-leaching technique for bone-tissue engineering. Field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy were used to observe the morphologies, pore structures of synthesized scaffolds, interactions between hydroxyapatite nanorods and poly(D,L) lactic acid, as well as the compositions of the scaffolds, respectively. Porosity of the scaffolds was determined using the liquid substitution method. Moreover, the apatite-forming capability of the scaffolds was evaluated through simulated body fluid (SBF) incubation tests, whereas the viability, attachment, and distribution of human osteoblast cells (MG 63 cell line) on the scaffolds were determined through alamarBlue assay and confocal laser microscopy after nuclear staining with 4',6-diamidino-2-phenylindole and actin filaments of a cytoskeleton with Oregon Green 488 phalloidin. Results showed that hydroxyapatite nanorod/poly(D,L) lactic acid scaffolds that mimic the structure of natural bone were successfully produced. These scaffolds possessed macropore networks with high porosity (80-84%) and mean pore sizes ranging 117-183 μm. These scaffolds demonstrated excellent apatite-forming capabilities. The rapid formation of bone-like apatites with flower-like morphology was observed after 7 days of incubation in SBFs. The scaffolds that had a high percentage (30 wt.%) of hydroxyapatite demonstrated better cell adhesion, proliferation, and distribution than those with low percentages of hydroxyapatite as the days of culture increased. This work presented an efficient route for developing biomimetic composite scaffolds, which have potential applications in bone-tissue engineering. PMID:25791418

Calcium and apatite granulations are demonstrated here to form in both human and fetal bovine serum in response to the simple addition of either calcium or phosphate, or a combination of both. These granulations are shown to represent precipitating complexes of protein and hydroxyapatite (HAP) that display marked pleomorphism, appearing as round, laminated particles, spindles, and films. These same complexes can be found in normal untreated serum, albeit at much lower amounts, and appear to result from the progressive binding of serum proteins with apatite until reaching saturation, upon which the mineralo-protein complexes precipitate. Chemically and morphologically, these complexes are virtually identical to the so-called nanobacteria (NB) implicated in numerous diseases and considered unusual for their small size, pleomorphism, and the presence of HAP. Like NB, serum granulations can seed particles upon transfer to serum-free medium, and their main protein constituents include albumin, complement components 3 and 4A, fetuin-A, and apolipoproteins A1 and B100, as well as other calcium and apatite binding proteins found in the serum. However, these serum mineralo-protein complexes are formed from the direct chemical binding of inorganic and organic phases, bypassing the need for any biological processes, including the long cultivation in cell culture conditions deemed necessary for the demonstration of NB. Thus, these serum granulations may result from physiologically inherent processes that become amplified with calcium phosphate loading or when subjected to culturing in medium. They may be viewed as simple mineralo-protein complexes formed from the deployment of calcification-inhibitory pathways used by the body to cope with excess calcium phosphate so as to prevent unwarranted calcification. Rather than representing novel pathophysiological mechanisms or exotic lifeforms, these results indicate that the entities described earlier as NB most likely originate

Titanite and apatite fission track (FT) thermochronology from 53 basement outcrops in southwest Madagascar reveal a protracted post Pan-African history of extensional tectonism, denudation and sedimentation. The titanite FT ages range between 276 ± 14 Ma and 379 ± 38 Ma. Apatite FT ages vary between 117 ± 26 Ma and 379 ± 19 Ma with mean track length scattering between 11.7 ± 0.59 μm and 13.74 ± 0.21 μm. Combined titanite and apatite FT data were used to calculate denudation rates. Samples from the paleo western margin of Madagascar along the N-S striking Pan-African Ejeda shear zone give above-average denudation rates (100-205 mMa-1) during Carboniferous times. The shear zone was probably reactivated during this times. In contrast the calculated denudation rates for samples from the interior of the island are moderate (25-120 mMa-1). Vitrinite reflectance data from the Sakoa coal area as well as titanite and apatite FT data imply that during the Permo-Triassic rifting, the areas along the paleo western margin that previously underwent fast denudation were buried by a sedimentary cover of up to ˜4.5 km. At this time, a graben developed further inland along the NW-SE striking transcontinental Bongolava-Ranotsara shear zone (BRSZ). Modelled time-temperature paths indicate that the area within the BRSZ remained cool and unaffected since Carboniferous times whereas the samples northeast and southwest of the BRSZ suggest phases of differential cooling during Permian-Triassic times. Seismic data from the Morondava basin indicate that during the Middle Jurassic drift between Madagascar and East-Africa a rift jump towards the west occurred. Modelled time-temperature histories of basement units from the paleo western margin, buried during Permo Triassic times, were exhumed during Jurassic times. This is most probably related with the modified rift kinematics and the associated southwest migration of the margin. Modelled time-temperature paths of all samples from

We present the zircon-apatite U-Pb ages and zircon Hf isotope composition of the granite batholith exposed at the western boundary of Chihuahua. Granidiorite samples were analyzed from both, north and south of the Rio El Fuerte and Sinforosa Lineament. Based on previous studies, the WWN-EES trending Sinforosa Lineament is proposed as the manifestation of a terrane boundary between Seri in the north and Tahue terrane in the south. Zircon U-Pb data indicate that the magmatism spans a time period of 36 Ma from 89 to 53 Ma to the north of the Sinforosa Lineament while granodiorites in the south of the Sinforosa Lineament are dated at 59 Ma. The U-Pb apatite ages are variable in the north of the Sinforosa Lineament and range from 86-51 Ma. These apatite dates are 1-28 Ma younger than the corresponding zircon U-Pb crystallization ages. This indicates variable cooling rates and moderate to shallow emplacement. In contrast, in the south of the Sinforosa Lineament, the U-Pb apatite ages (64-59 Ma) are indistinguishable from the zircon U-Pb age (59 Ma), indicating rapid cooling and shallow emplacement. Zircon morphology and U-Pb dating revealed the absence of inherited component in the zircon ages, as no inheritance of any age has been observed. Most of the northwestern Mexico is underlain by Precambrian-Paleozoic-Jurassic basement. However, in the study area, U-Pb dating does not support the involvement of the older basement in generating the granite magmas. The weighted mean initial ɛHf (t) isotope composition of granodiorites on both sides of the Sinforosa Lineament varies from +2 to +5. However, Hf isotope composition in the south of the Sinforosa Lineament is more heterogeneous and relatively evolved with weighted Mean ɛHf (t) = +1.45. The Hf isotope composition is consistent with the previously reported near bulk silicate Sr-Nd isotope values. We suggest that the magmatic rocks in this region are not derived from melting of a felsic older crust beneath the batholith

Calcium and apatite granulations are demonstrated here to form in both human and fetal bovine serum in response to the simple addition of either calcium or phosphate, or a combination of both. These granulations are shown to represent precipitating complexes of protein and hydroxyapatite (HAP) that display marked pleomorphism, appearing as round, laminated particles, spindles, and films. These same complexes can be found in normal untreated serum, albeit at much lower amounts, and appear to result from the progressive binding of serum proteins with apatite until reaching saturation, upon which the mineralo-protein complexes precipitate. Chemically and morphologically, these complexes are virtually identical to the so-called nanobacteria (NB) implicated in numerous diseases and considered unusual for their small size, pleomorphism, and the presence of HAP. Like NB, serum granulations can seed particles upon transfer to serum-free medium, and their main protein constituents include albumin, complement components 3 and 4A, fetuin-A, and apolipoproteins A1 and B100, as well as other calcium and apatite binding proteins found in the serum. However, these serum mineralo-protein complexes are formed from the direct chemical binding of inorganic and organic phases, bypassing the need for any biological processes, including the long cultivation in cell culture conditions deemed necessary for the demonstration of NB. Thus, these serum granulations may result from physiologically inherent processes that become amplified with calcium phosphate loading or when subjected to culturing in medium. They may be viewed as simple mineralo-protein complexes formed from the deployment of calcification-inhibitory pathways used by the body to cope with excess calcium phosphate so as to prevent unwarranted calcification. Rather than representing novel pathophysiological mechanisms or exotic lifeforms, these results indicate that the entities described earlier as NB most likely originate

Erosion in the Himalaya is driven largely by a strongly coupled system of extreme climatic conditions and active tectonic processes. Spatial and temporal variations in erosion rates along strike are presumably controlled by differences in local climate, seismicity, deformation rates, and lithology. Quantifying the contribution of each of these parameters to the erosional budget of the Himalaya, however, is a nontrivial problem. The easternmost portion of the Himalayan arc offers a natural laboratory to explore the role of climatic influence on erosion rates. Deformation and uplift of the Shillong Plateau since ~8 Ma has created an orographic barrier ~400 km long that shields the eastern Himalaya, in Arunachal Pradesh, India, from a significant proportion of the precipitation carried by the South Asian Monsoon. Long-term exhumation rates derived from the Himalaya west and east of this orographic barrier have been shown to differ by a factor of ~2, a difference ascribed to reduced climatic forcing of erosion in the lee of the Shillong Plateau. Here we present apatite (U-Th)/He thermochronology data from modern detrital samples collected from northeast India. Between 18-20 single grain ages from each catchment were analyzed in order to calculate erosion rates on a 106 yr timescale. Recently developed Bayesian techniques for the inverse modeling of detrital data were used to derive time-temperature histories for each sample. Recent erosion rates modeled for a single south-facing catchment on the Shillong Plateau are modest, ~0.25 km Myr-1, and show a clear increase in exhumation rates at ~8 Ma from rates of <0.01 km Myr-1. These results are consistent with published estimates based on bedrock thermochronology sampling. Detrital data from the Arunachal Himalaya also reveal an increase in exhumation rate, from ~0.01 to ~0.55 km Myr-1, at ~7 Ma. While these rates are consistent with erosion rates derived from bedrock samples in the lee of the Shillong Plateau in the

In recent years, biomimetic synthetic apatite nanoparticles (AP-NPs), having chemical similarity with the mineral phase of bone, have attracted a great interest in nanomedicine as potential drug carriers. To evaluate the therapeutic perspectives of AP-NPs through the mechanisms of action and organs they interact with, the noninvasive monitoring of their in vivo behavior is of paramount importance. To this aim, here the feasibility to radiolabel AP-NPs ("naked" and surface-modified with citrate to reduce their aggregation) with two positron emission tomographic (PET) imaging agents ([(18)F]NaF and (68)Ga-NO2AP(BP)) was investigated. [(18)F]NaF was used for the direct incorporation of the radioisotope into the crystal lattice, while the labeling by surface functionalization was accomplished by using (68)Ga-NO2AP(BP) (a new radio-metal chelating agent). The labeling results with both tracers were fast, straightforward, and reproducible. AP-NPs demonstrated excellent ability to bind relevant quantities of both radiotracers and good in vitro stability in clinically relevant media after the labeling. In vivo PET studies in healthy Wistar rats established that the radiolabeled AP-NPs gave significant PET signals and they were stable over the investigated time (90 min) since any tracer desorption was detected. These preliminary in vivo studies furthermore showed a clear ability of citrated versus naked AP-NPs to accumulate in different organs. Interestingly, contrary to naked AP-NPs, citrated ones, which unveiled higher colloidal stability in aqueous suspensions, were able to escape the first physiological filter, i.e., the lungs, being then accumulated in the liver and, to a lesser extent, in the spleen. The results of this work, along with the fact that AP-NPs can be also functionalized with targeting ligands, with therapeutic agents, and also with metals for a combination of different imaging modalities, make AP-NPs very encouraging materials for further investigations

In this study, we investigated self-organized TiO{sub 2} nanotubes that were grown using anodization of commercially pure titanium at 5 V or 10 V in NH{sub 4}F/NaCl electrolyte. The nanotube arrays were annealed at 450 °C for 3 h to convert the amorphous nanotubes to anatase and then they were immersed in simulated body fluid at 37 °C for 0.5, 1, and 14 days. The purpose of this experiment was to evaluate the apatite-formation abilities of anodized Ti nanotubes with different tube diameters and lengths. The nanotubes that formed on the surfaces of Ti were examined using a field emission scanning electron microscope, X-ray diffraction, and X-ray photoelectron spectroscope. When the anodizing potential was increased from 5 V to 10 V, the pore diameter of the nanotube increased from approximately 24–30 nm to 35–53 nm, and the tube length increased from approximately 590 nm to 730 nm. In vitro testing of the heat-treated nanotube arrays indicated that Ca-P formation occurred after only 1 day of immersion in simulated body fluid. This result was particularly apparent in the samples that were anodized at 10 V. It was also found that the thickness of the Ca-P layer increases as the applied potential for anodized c.p. Ti increases. The average thickness of the Ca-P layer on Ti that was anodized at 5 V and 10 V was approximately 170 nm and 190 nm, respectively, after immersion in simulated body fluid for 14 days. - Highlights: • TiO{sub 2} nanotube on Ti surface was formed by anodic oxidation in a NaCl/NH{sub 4}F solution. • TiO{sub 2} layers show a tube length of 590 nm and 730 nm at 5 V and 10 V, respectively. • After soaking in SBF, Ca-P layer completely covered the entire nanotubular surfaces. • The Ca-P layer was thicker on the Ti surface anodized at 10 V.

The Tongshi intrusive complex from the southeastern margin of the North China Craton is composed of syenite and monzonite, and was emplaced at ca. 180 Ma. Apatite from the syenite and monzonite were analyzed to better understand the petrogenesis of the complex and its mineralization potential. The cathodoluminescence images of some apatites from the monzonite exhibit core-rim texture, whereas the apatites from the syenite display uniform inner texture. The core and rim domains of the apatites exhibit distinct Sr isotopes and major-trace element compositions, whereas only little variation is displayed by the oxygen isotopes. The core portions of the apatites were inferred to be inherited from the protolith of the monzonite during remelting process. The calculated δ18O values of the syenite range from 3.5‰ to 4.1‰ with an average of 3.8‰ (SE = 0.21), which is significantly lower than that of the monzonite sample (with a range of 6.4-6.9‰, and mean at 6.7‰). In conjunction with the heterogeneity of Nd isotopic compositions (with normalized 143Nd/144Nd ratios varying from 0.51151 to 0.51236, and εNd (t = 180 Ma) values from -20.3 to -4.8) of the apatites from the syenite, it is proposed that the syenite melts may have been contaminated by crustal components which were earlier hydrothermally altered at high temperature. Based on element diffusion theory, we calculate the temperature of this crustal contamination to be higher than 637 °C, the closure temperature of Sm-Nd isotopic diffusion in apatite, and estimate that the duration of this process is probably shorter than 0.13 Ma. The oxygen fugacity of the syenite and monzonite calculated by apatite Mn content indicate that high oxidization state of the syenite magma can enhance the metallic mineralization potential. In contrast, the lower oxygen fugacity of the monzonite melt was unfavorable for metal enrichment, thus leading to insignificant mineralization. Our study recommends more focus for gold

Effect of disodium EDTA (salt of ethylenediamine tetraacetic acid) on the crystallization of struvite and carbonate apatite was studied. To evaluate such an effect we performed an experiment of struvite and carbonate apatite growth from artificial urine. The crystallization process was induced by Proteus mirabilis to mimic the real urinary tract infection, which usually leads to urinary stone formation. The results demonstrate that disodium EDTA exhibits the effect against P. mirabilis retarding the activity of urease - an enzyme produced by these microorganisms. The spectrophotometric results demonstrate that, with and without P. mirabilis, the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). These results are discussed from the standpoint of speciation of complexes formed in the solution of artificial urine in the presence of disodium EDTA. The size of struvite crystals was found to decrease in the presence of disodium EDTA. However, struvite crystals are larger in the presence of bacteria while the crystal morphology and habit remain unchanged.

A novel method has been developed to rapidly deposit bone-like apatite with the assistance of ultraviolet (UV) light irradiation on the nanostructured titania in the simulated body fluid (SBF). The process has three main steps: Ti-24Nb-4Zr-7.9Sn alloy was heated at 650°C for 3 h, UV-light illumination in air for 4 h and soaking in the SBF for 3 d. A titania coating consisted of main rutile formed on the thermal oxidized Ti-24Nb-4Zr-7.9Sn alloy. The UV not only converted the rutile surface from hydrophilic to hydrophobic but also stimulated high surface activity. After 4 h UV illumination, the contents of Ti3+ and hydroxyl groups on the oxidized sample were increased, while that of lattice O decreased. After 3 d of soaking in the SBF, a compact and uniform layer of carbonated hydroxyapatite (CHA) particles was formed on the UV-illuminated rutile surface whereas there was a few of HA to be viewed on the surface of as-oxidized Ti-24Nb-4Zr-7.9Sn alloy. Our study demonstrates a simple, fast and cost-effective technique for growing bone-like apatite on titanium alloys.

Apatite and zircon grains separated from a sandstone layer of earliest Late Devonian age, Catskill Mountains, have been subjected to fission-track analysis. A 125-m.y. age, obtained on the apatite grains, requires a temperature for the sediment of less than 120 °C during the past 125 m.y. At some time prior to 125 m.y. ago, temperatures were above 120 °C long enough to cause complete fading of tracks. Analysis of zircon grains resulted in a fission-track age of 320 m.y. Zircon data indicate that the temperature of the sediment layer enclosing the grains did not exceed 175 to 200 °C over a 235-rn.y. period (time between sedimentation and 125 m.y. ago). If one assumes a typical geothermal gradient of 25 °C/km, a burial depth of between 4 and 7 km is indicated for the lowermost Upper Devonian, atskill Mountains. *Present address: Rensselaer Polytechnic Institute, Troy, New York 12181

In this paper the crystallization of a bioinspired citrate-functionalized apatite (cit-Ap) thin film (thickness about 2μm) on Ti-6Al-4V supports pre-coated with bioactive and corrosion resistant buffer layer of silicon nitride (Si3N4), silicon carbide (SiC) or titanium nitride (TiN) is reported. The apatitic coatings were produced by a new coating technique based on the induction heating of the implants immersed in a flowing calcium-citrate-phosphate solution at pH11. The influence of the buffer layers and the surface roughness of the substrate on the chemical-physical features and adhesion of the cit-Ap films were investigated. The best plasticity, compactness and adherence properties have been found in the Ap layer grown on Si3N4, followed by the Ap grown on SiC and TiN, respectively. The adhesion property was likely related to the roughness of the buffered substrates, whereas the compactness and plasticity were closely related to the operating conditions during the Ap crystallization (flow rate of the solution and increase of temperature) rather than to the nature of the buffer layer. PMID:23648093